JP6770217B2 - A method for producing a solid electrolytic capacitor and a method for producing a dispersion containing a conjugated conductive polymer. - Google Patents
A method for producing a solid electrolytic capacitor and a method for producing a dispersion containing a conjugated conductive polymer. Download PDFInfo
- Publication number
- JP6770217B2 JP6770217B2 JP2020510964A JP2020510964A JP6770217B2 JP 6770217 B2 JP6770217 B2 JP 6770217B2 JP 2020510964 A JP2020510964 A JP 2020510964A JP 2020510964 A JP2020510964 A JP 2020510964A JP 6770217 B2 JP6770217 B2 JP 6770217B2
- Authority
- JP
- Japan
- Prior art keywords
- dispersion
- solid electrolytic
- substituent
- electrolytic capacitor
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000006185 dispersion Substances 0.000 title claims description 218
- 229920001940 conductive polymer Polymers 0.000 title claims description 112
- 239000007787 solid Substances 0.000 title claims description 94
- 239000003990 capacitor Substances 0.000 title claims description 91
- 238000004519 manufacturing process Methods 0.000 title claims description 63
- 239000007788 liquid Substances 0.000 claims description 123
- 150000001875 compounds Chemical class 0.000 claims description 110
- 229920000447 polyanionic polymer Polymers 0.000 claims description 94
- 239000000178 monomer Substances 0.000 claims description 80
- -1 salt compound Chemical class 0.000 claims description 69
- 239000002245 particle Substances 0.000 claims description 64
- 125000001424 substituent group Chemical group 0.000 claims description 61
- 239000012736 aqueous medium Substances 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000007784 solid electrolyte Substances 0.000 claims description 22
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000000623 heterocyclic group Chemical group 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000010130 dispersion processing Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 9
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 229930192474 thiophene Natural products 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000002609 medium Substances 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 21
- 230000001681 protective effect Effects 0.000 description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 125000004093 cyano group Chemical group *C#N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 230000008719 thickening Effects 0.000 description 10
- 229920003169 water-soluble polymer Polymers 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000003021 water soluble solvent Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 238000011033 desalting Methods 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 7
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 7
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 7
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 125000001072 heteroaryl group Chemical group 0.000 description 6
- 229920000123 polythiophene Polymers 0.000 description 6
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 229920001281 polyalkylene Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 125000005385 peroxodisulfate group Chemical group 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000000532 dioxanyl group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MUZIZEZCKKMZRT-UHFFFAOYSA-N 1,2-dithiolane Chemical group C1CSSC1 MUZIZEZCKKMZRT-UHFFFAOYSA-N 0.000 description 2
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- IHCCAYCGZOLTEU-UHFFFAOYSA-N 3-furoic acid Chemical compound OC(=O)C=1C=COC=1 IHCCAYCGZOLTEU-UHFFFAOYSA-N 0.000 description 2
- INZDUCBKJIQWBX-UHFFFAOYSA-N 3-hexoxy-4-methyl-1h-pyrrole Chemical compound CCCCCCOC1=CNC=C1C INZDUCBKJIQWBX-UHFFFAOYSA-N 0.000 description 2
- RFSKGCVUDQRZSD-UHFFFAOYSA-N 3-methoxythiophene Chemical compound COC=1C=CSC=1 RFSKGCVUDQRZSD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- DGDSVFZDNDFBNL-UHFFFAOYSA-H iron(3+);trisulfate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DGDSVFZDNDFBNL-UHFFFAOYSA-H 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 150000003230 pyrimidines Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KQBSGRWMSNFIPG-UHFFFAOYSA-N trioxane Chemical group C1COOOC1 KQBSGRWMSNFIPG-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DCNHQNGFLVPROM-QXMHVHEDSA-N (z)-n,n-dimethyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)C DCNHQNGFLVPROM-QXMHVHEDSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- ZPOROQKDAPEMOL-UHFFFAOYSA-N 1h-pyrrol-3-ol Chemical compound OC=1C=CNC=1 ZPOROQKDAPEMOL-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- LECMBPWEOVZHKN-UHFFFAOYSA-N 2-(2-chloroethoxy)ethanol Chemical compound OCCOCCCl LECMBPWEOVZHKN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- KECMLGZOQMJIBM-UHFFFAOYSA-N 2-[2-(2-chloroethoxy)ethoxy]ethanol Chemical compound OCCOCCOCCCl KECMLGZOQMJIBM-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical group O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- ONJRTQUWKRDCTA-UHFFFAOYSA-N 2h-thiochromene Chemical group C1=CC=C2C=CCSC2=C1 ONJRTQUWKRDCTA-UHFFFAOYSA-N 0.000 description 1
- XWEYATZFSPHATJ-UHFFFAOYSA-N 3,4-dibutoxythiophene Chemical compound CCCCOC1=CSC=C1OCCCC XWEYATZFSPHATJ-UHFFFAOYSA-N 0.000 description 1
- LGPVKMIWERPYIJ-UHFFFAOYSA-N 3,4-dibutyl-1h-pyrrole Chemical compound CCCCC1=CNC=C1CCCC LGPVKMIWERPYIJ-UHFFFAOYSA-N 0.000 description 1
- FKXCQUBXKMXXBG-UHFFFAOYSA-N 3,4-dibutylthiophene Chemical compound CCCCC1=CSC=C1CCCC FKXCQUBXKMXXBG-UHFFFAOYSA-N 0.000 description 1
- CFCYZQALCKXBOZ-UHFFFAOYSA-N 3,4-didecoxythiophene Chemical compound CCCCCCCCCCOC1=CSC=C1OCCCCCCCCCC CFCYZQALCKXBOZ-UHFFFAOYSA-N 0.000 description 1
- GVQISPCTVFFREP-UHFFFAOYSA-N 3,4-didodecoxythiophene Chemical compound CCCCCCCCCCCCOC1=CSC=C1OCCCCCCCCCCCC GVQISPCTVFFREP-UHFFFAOYSA-N 0.000 description 1
- MFRXQRCKOQUENC-UHFFFAOYSA-N 3,4-diethoxythiophene Chemical compound CCOC1=CSC=C1OCC MFRXQRCKOQUENC-UHFFFAOYSA-N 0.000 description 1
- BUZZAMRHHXZQNN-UHFFFAOYSA-N 3,4-diheptoxythiophene Chemical compound CCCCCCCOC1=CSC=C1OCCCCCCC BUZZAMRHHXZQNN-UHFFFAOYSA-N 0.000 description 1
- OMANTHZRUHGCNC-UHFFFAOYSA-N 3,4-dihexoxythiophene Chemical compound CCCCCCOC1=CSC=C1OCCCCCC OMANTHZRUHGCNC-UHFFFAOYSA-N 0.000 description 1
- WNOOCRQGKGWSJE-UHFFFAOYSA-N 3,4-dihydro-2h-thieno[3,4-b][1,4]dioxepine Chemical compound O1CCCOC2=CSC=C21 WNOOCRQGKGWSJE-UHFFFAOYSA-N 0.000 description 1
- ZUDCKLVMBAXBIF-UHFFFAOYSA-N 3,4-dimethoxythiophene Chemical compound COC1=CSC=C1OC ZUDCKLVMBAXBIF-UHFFFAOYSA-N 0.000 description 1
- OJFOWGWQOFZNNJ-UHFFFAOYSA-N 3,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC=C1C OJFOWGWQOFZNNJ-UHFFFAOYSA-N 0.000 description 1
- GPSFYJDZKSRMKZ-UHFFFAOYSA-N 3,4-dimethylthiophene Chemical compound CC1=CSC=C1C GPSFYJDZKSRMKZ-UHFFFAOYSA-N 0.000 description 1
- OTUYNPNPIIFVGN-UHFFFAOYSA-N 3,4-dioctoxythiophene Chemical compound CCCCCCCCOC1=CSC=C1OCCCCCCCC OTUYNPNPIIFVGN-UHFFFAOYSA-N 0.000 description 1
- LKYDJXOAZWBJIM-UHFFFAOYSA-N 3,4-dipropoxythiophene Chemical compound CCCOC1=CSC=C1OCCC LKYDJXOAZWBJIM-UHFFFAOYSA-N 0.000 description 1
- JSOMPMRZESLPSM-UHFFFAOYSA-N 3-(2-methylpropyl)aniline Chemical compound CC(C)CC1=CC=CC(N)=C1 JSOMPMRZESLPSM-UHFFFAOYSA-N 0.000 description 1
- FYMPIGRRSUORAR-UHFFFAOYSA-N 3-(4-methyl-1h-pyrrol-3-yl)propanoic acid Chemical compound CC1=CNC=C1CCC(O)=O FYMPIGRRSUORAR-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 1
- FCVHZARBOWEONP-UHFFFAOYSA-N 3-butoxy-1h-pyrrole Chemical compound CCCCOC=1C=CNC=1 FCVHZARBOWEONP-UHFFFAOYSA-N 0.000 description 1
- NZSSXTMHSXMZBL-UHFFFAOYSA-N 3-butoxythiophene Chemical compound CCCCOC=1C=CSC=1 NZSSXTMHSXMZBL-UHFFFAOYSA-N 0.000 description 1
- ATWNFFKGYPYZPJ-UHFFFAOYSA-N 3-butyl-1h-pyrrole Chemical compound CCCCC=1C=CNC=1 ATWNFFKGYPYZPJ-UHFFFAOYSA-N 0.000 description 1
- KPOCSQCZXMATFR-UHFFFAOYSA-N 3-butylthiophene Chemical compound CCCCC=1C=CSC=1 KPOCSQCZXMATFR-UHFFFAOYSA-N 0.000 description 1
- QUBJDMPBDURTJT-UHFFFAOYSA-N 3-chlorothiophene Chemical compound ClC=1C=CSC=1 QUBJDMPBDURTJT-UHFFFAOYSA-N 0.000 description 1
- YTIXUMPBYXTWQA-UHFFFAOYSA-N 3-decoxythiophene Chemical compound CCCCCCCCCCOC=1C=CSC=1 YTIXUMPBYXTWQA-UHFFFAOYSA-N 0.000 description 1
- FFRZVVFLHHGORC-UHFFFAOYSA-N 3-decyl-1h-pyrrole Chemical compound CCCCCCCCCCC=1C=CNC=1 FFRZVVFLHHGORC-UHFFFAOYSA-N 0.000 description 1
- JAYBIBLZTQMCAY-UHFFFAOYSA-N 3-decylthiophene Chemical compound CCCCCCCCCCC=1C=CSC=1 JAYBIBLZTQMCAY-UHFFFAOYSA-N 0.000 description 1
- HQKVUWMATDWFJI-UHFFFAOYSA-N 3-dodecoxythiophene Chemical compound CCCCCCCCCCCCOC=1C=CSC=1 HQKVUWMATDWFJI-UHFFFAOYSA-N 0.000 description 1
- HGICMYITGGLHHY-UHFFFAOYSA-N 3-dodecyl-1h-pyrrole Chemical compound CCCCCCCCCCCCC=1C=CNC=1 HGICMYITGGLHHY-UHFFFAOYSA-N 0.000 description 1
- RFKWIEFTBMACPZ-UHFFFAOYSA-N 3-dodecylthiophene Chemical compound CCCCCCCCCCCCC=1C=CSC=1 RFKWIEFTBMACPZ-UHFFFAOYSA-N 0.000 description 1
- KEAYXGHOGPUYPB-UHFFFAOYSA-N 3-ethoxy-1h-pyrrole Chemical compound CCOC=1C=CNC=1 KEAYXGHOGPUYPB-UHFFFAOYSA-N 0.000 description 1
- ZFQVXRBCYGOGAA-UHFFFAOYSA-N 3-ethoxy-4-methylthiophene Chemical compound CCOC1=CSC=C1C ZFQVXRBCYGOGAA-UHFFFAOYSA-N 0.000 description 1
- RDEGOEYUQCUBPE-UHFFFAOYSA-N 3-ethoxythiophene Chemical compound CCOC=1C=CSC=1 RDEGOEYUQCUBPE-UHFFFAOYSA-N 0.000 description 1
- RLLBWIDEGAIFPI-UHFFFAOYSA-N 3-ethyl-1h-pyrrole Chemical compound CCC=1C=CNC=1 RLLBWIDEGAIFPI-UHFFFAOYSA-N 0.000 description 1
- SLDBAXYJAIRQMX-UHFFFAOYSA-N 3-ethylthiophene Chemical compound CCC=1C=CSC=1 SLDBAXYJAIRQMX-UHFFFAOYSA-N 0.000 description 1
- JFRPBGLJDHIQGT-UHFFFAOYSA-N 3-heptoxythiophene Chemical compound CCCCCCCOC=1C=CSC=1 JFRPBGLJDHIQGT-UHFFFAOYSA-N 0.000 description 1
- IUUMHORDQCAXQU-UHFFFAOYSA-N 3-heptylthiophene Chemical compound CCCCCCCC=1C=CSC=1 IUUMHORDQCAXQU-UHFFFAOYSA-N 0.000 description 1
- IOKBHBPVRURKRQ-UHFFFAOYSA-N 3-hexoxy-1h-pyrrole Chemical compound CCCCCCOC=1C=CNC=1 IOKBHBPVRURKRQ-UHFFFAOYSA-N 0.000 description 1
- GFJHLDVJFOQWLT-UHFFFAOYSA-N 3-hexoxythiophene Chemical compound CCCCCCOC=1C=CSC=1 GFJHLDVJFOQWLT-UHFFFAOYSA-N 0.000 description 1
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 1
- WGKRMQIQXMJVFZ-UHFFFAOYSA-N 3-iodothiophene Chemical compound IC=1C=CSC=1 WGKRMQIQXMJVFZ-UHFFFAOYSA-N 0.000 description 1
- OTODBDQJLMYYKQ-UHFFFAOYSA-N 3-methoxy-1h-pyrrole Chemical compound COC=1C=CNC=1 OTODBDQJLMYYKQ-UHFFFAOYSA-N 0.000 description 1
- HGDGACBSGVRCSM-UHFFFAOYSA-N 3-methoxy-4-methylthiophene Chemical compound COC1=CSC=C1C HGDGACBSGVRCSM-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 1
- OIXVNYHVHGWVEN-UHFFFAOYSA-N 3-methyl-5-(1h-pyrrol-2-yl)pentanoic acid Chemical compound OC(=O)CC(C)CCC1=CC=CN1 OIXVNYHVHGWVEN-UHFFFAOYSA-N 0.000 description 1
- GRTWOPGOPPTXOA-UHFFFAOYSA-N 3-methyl-5-thiophen-2-ylpentanoic acid Chemical compound OC(=O)CC(C)CCC1=CC=CS1 GRTWOPGOPPTXOA-UHFFFAOYSA-N 0.000 description 1
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 description 1
- KPORMHZYIJPHAV-UHFFFAOYSA-N 3-octadecoxythiophene Chemical compound CCCCCCCCCCCCCCCCCCOC=1C=CSC=1 KPORMHZYIJPHAV-UHFFFAOYSA-N 0.000 description 1
- ARFJPHXJBIEWSZ-UHFFFAOYSA-N 3-octadecylthiophene Chemical compound CCCCCCCCCCCCCCCCCCC=1C=CSC=1 ARFJPHXJBIEWSZ-UHFFFAOYSA-N 0.000 description 1
- AUVZKIJQGLYISA-UHFFFAOYSA-N 3-octoxythiophene Chemical compound CCCCCCCCOC=1C=CSC=1 AUVZKIJQGLYISA-UHFFFAOYSA-N 0.000 description 1
- WFHVTZRAIPYMMO-UHFFFAOYSA-N 3-octyl-1h-pyrrole Chemical compound CCCCCCCCC=1C=CNC=1 WFHVTZRAIPYMMO-UHFFFAOYSA-N 0.000 description 1
- WQYWXQCOYRZFAV-UHFFFAOYSA-N 3-octylthiophene Chemical compound CCCCCCCCC=1C=CSC=1 WQYWXQCOYRZFAV-UHFFFAOYSA-N 0.000 description 1
- ZDQZVKVIYAPRON-UHFFFAOYSA-N 3-phenylthiophene Chemical compound S1C=CC(C=2C=CC=CC=2)=C1 ZDQZVKVIYAPRON-UHFFFAOYSA-N 0.000 description 1
- FAOPZUAEZGKQNC-UHFFFAOYSA-N 3-propyl-1h-pyrrole Chemical compound CCCC=1C=CNC=1 FAOPZUAEZGKQNC-UHFFFAOYSA-N 0.000 description 1
- QZNFRMXKQCIPQY-UHFFFAOYSA-N 3-propylthiophene Chemical compound CCCC=1C=CSC=1 QZNFRMXKQCIPQY-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FXPOCCDGHHTZAO-UHFFFAOYSA-N 4-methyl-1h-pyrrole-3-carboxylic acid Chemical compound CC1=CNC=C1C(O)=O FXPOCCDGHHTZAO-UHFFFAOYSA-N 0.000 description 1
- LRFIHWGUGBXFEC-UHFFFAOYSA-N 4-methylthiophene-3-carboxylic acid Chemical compound CC1=CSC=C1C(O)=O LRFIHWGUGBXFEC-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- GZPTUJPYUAZIID-UHFFFAOYSA-N 5-ethyl-4-methylthiophene-3-carboxylic acid Chemical compound CCC=1SC=C(C(O)=O)C=1C GZPTUJPYUAZIID-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000025174 PANDAS Diseases 0.000 description 1
- 208000021155 Paediatric autoimmune neuropsychiatric disorders associated with streptococcal infection Diseases 0.000 description 1
- 240000000220 Panda oleosa Species 0.000 description 1
- 235000016496 Panda oleosa Nutrition 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical group N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical group C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001719 carbohydrate derivatives Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- ICZKASVWFUJTEI-UHFFFAOYSA-N n,n-dimethyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN(C)C ICZKASVWFUJTEI-UHFFFAOYSA-N 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- ATBNMWWDBWBAHM-UHFFFAOYSA-N n-decyl-n-methyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCCCCC ATBNMWWDBWBAHM-UHFFFAOYSA-N 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002850 poly(3-methoxythiophene) polymer Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- DOYOPBSXEIZLRE-UHFFFAOYSA-N pyrrole-3-carboxylic acid Chemical compound OC(=O)C=1C=CNC=1 DOYOPBSXEIZLRE-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- HERSKCAGZCXYMC-UHFFFAOYSA-N thiophen-3-ol Chemical compound OC=1C=CSC=1 HERSKCAGZCXYMC-UHFFFAOYSA-N 0.000 description 1
- MPKQTNAUFAZSIJ-UHFFFAOYSA-N thiophene-3,4-diol Chemical compound OC1=CSC=C1O MPKQTNAUFAZSIJ-UHFFFAOYSA-N 0.000 description 1
- GSXCEVHRIVLFJV-UHFFFAOYSA-N thiophene-3-carbonitrile Chemical compound N#CC=1C=CSC=1 GSXCEVHRIVLFJV-UHFFFAOYSA-N 0.000 description 1
- YNVOMSDITJMNET-UHFFFAOYSA-N thiophene-3-carboxylic acid Chemical compound OC(=O)C=1C=CSC=1 YNVOMSDITJMNET-UHFFFAOYSA-N 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical group S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical group C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、固体電解コンデンサの製造方法、及び共役系導電性重合体を含有する分散液の製造方法に関する。 The present invention relates to a method for producing a solid electrolytic capacitor and a method for producing a dispersion liquid containing a conjugated conductive polymer.
金属表面に陽極酸化によって誘電体酸化被膜を形成し、これに固体電解質を接触させて製造され、固体電解質として導電性高分子を用いた固体電解コンデンサが提案されている。 A solid electrolytic capacitor has been proposed in which a dielectric oxide film is formed on a metal surface by anodization and a solid electrolyte is brought into contact with the film, and a conductive polymer is used as the solid electrolyte.
陽極酸化による誘電体酸化被膜で被われる金属の例として、アルミニウム、タンタル、ニオブ等が知られている。
また、固体電解コンデンサに用いられる導電性高分子として、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレン、ポリフェニレン、ポリ(p−フェニレン−ビニレン)、ポリアセン、ポリチオフェンビニレン及びその誘導体等の共役系導電性重合体が知られている。また、上記共役系導電性重合体の対アニオンとしてポリスチレンスルホン酸等のポリアニオンを共役系導電性重合体へドープする技術が知られている。Aluminum, tantalum, niobium and the like are known as examples of metals covered with a dielectric oxide film by anodization.
Conjugated conductive polymers such as polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene, poly (p-phenylene-vinylene), polyacene, polythiophene vinylene and derivatives thereof are known as conductive polymers used in solid electrolytic capacitors. Has been done. Further, a technique of doping a conjugated conductive polymer with a polyanion such as polystyrene sulfonic acid as a counter anion of the conjugated conductive polymer is known.
固体電解質の一般的な形成方法としては、弁作用を有する金属(弁作用金属)表面に形成した誘電体酸化被膜上で、単量体化合物溶液と酸化剤溶液とを化学酸化重合する、もしくは電解重合する方法が挙げられる。また、固体電解質の形成方法として、導電性高分子水溶液もしくは懸濁液を、誘電体酸化被膜が形成された弁作用金属に塗布する方法が提案されている。 As a general method for forming a solid electrolyte, a monomer compound solution and an oxidizing agent solution are chemically oxidatively polymerized or electrolyzed on a dielectric oxide film formed on the surface of a metal having a valve action (valve action metal). Examples include a method of polymerization. Further, as a method for forming a solid electrolyte, a method of applying a conductive polymer aqueous solution or suspension to a valve acting metal on which a dielectric oxide film is formed has been proposed.
例えば、特許文献1には、コンデンサ素子に導電性高分子の微粒子を分散させた導電性高分子分散水溶液を含浸させて第1の固体電解質層を形成する工程と、この第1の固体電解質層の表面に、複素環式モノマーを含有する溶液と酸化剤を含有する溶液を個々に含浸することにより、または複素環式モノマーと酸化剤を含有する混合溶液を含浸することにより第2の固体電解質層を形成する工程とを具備した固体電解コンデンサの製造方法が開示されている。
For example,
特許文献2には、弁金属粉末を焼結してなる焼結体の表面に誘電体酸化皮膜を形成したコンデンサ素子に、固体電解質層として重合性モノマーの化学重合により導電性高分子層を形成した後、このコンデンサ素子を導電性高分子溶液に浸漬、または導電性高分子溶液を塗布し乾燥する工程を含む固体電解コンデンサの製造方法が開示されている。 In Patent Document 2, a conductive polymer layer is formed as a solid electrolyte layer by chemically polymerizing a polymerizable monomer on a capacitor element having a dielectric oxide film formed on the surface of a sintered body obtained by sintering a valve metal powder. After that, a method for manufacturing a solid electrolytic capacitor including a step of immersing the capacitor element in a conductive polymer solution or applying a conductive polymer solution and drying the capacitor element is disclosed.
特許文献3では、ポリ(3,4−エチレンジオキシチオフェン)−ポリスチレンスルホン酸(PEDOT−PSS)を、超音波照射を用いて重合するプロセスが提案されている。 Patent Document 3 proposes a process of polymerizing poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT-PSS) by using ultrasonic irradiation.
特許文献4には、単量体化合物とポリアニオンにより保護コロイド化されたシード粒子を含む分散媒中で、単量体化合物を重合して共役系導電性重合体含有分散液を得る工程が開示されている。 Patent Document 4 discloses a step of polymerizing a monomer compound in a dispersion medium containing seed particles protected and colloidalized with a monomer compound and a polyanion to obtain a conjugated conductive polymer-containing dispersion. ing.
しかし、これらの従来技術には、容量発現率(静電容量)及び等価直列抵抗(ESR)の性能をさらに改善する余地があった。
本発明は、容量発現率(静電容量)が高く、かつ等価直列抵抗(ESR)が低い固体電解コンデンサ、およびその製造方法を提供することを目的とする。
さらに本発明は、容量発現率(静電容量)が高く、かつ等価直列抵抗(ESR)が低い固体電解コンデンサの製造に有用な、共役系導電性重合体を含有する分散液の製造方法を提供することを目的とする。However, these prior arts have room for further improvement in capacity expression rate (capacitance) and equivalent series resistance (ESR) performance.
An object of the present invention is to provide a solid electrolytic capacitor having a high capacitance expression rate (capacitance) and a low equivalent series resistance (ESR), and a method for manufacturing the same.
Further, the present invention provides a method for producing a dispersion liquid containing a conjugated conductive polymer, which is useful for producing a solid electrolytic capacitor having a high capacitance expression rate (capacitance) and a low equivalent series resistance (ESR). The purpose is to do.
本発明者らは、鋭意研究を重ねた結果、固体電解コンデンサの固体電解質として用いる共役系導電性重合体分散液の製造過程において、共役系導電性重合体とポリアニオンとが形成する複合体の解凝集を効率的に行うために、これらを含む分散液に対する分散処理を一時停止することで、上記課題を解決し得ることを見出し、本発明を完成した。 As a result of diligent research, the present inventors have solved the complex formed by the conjugated conductive polymer and the polyanion in the manufacturing process of the conjugated conductive polymer dispersion used as the solid electrolyte of the solid electrolytic capacitor. We have found that the above problems can be solved by suspending the dispersion treatment of the dispersion liquid containing these in order to efficiently perform the aggregation, and completed the present invention.
すなわち、本発明は下記[1]〜[15]の固体電解コンデンサの製造方法及び固体電解コンデンサ、並びに下記[16]の共役系導電性重合体を含有する分散液の製造方法に関する。
[1]
表面に誘電体被膜を有する弁作用金属からなる多孔性陽極体と、前記誘電体被膜の表面に設けられた固体電解質層とを有する固体電解コンデンサの製造方法であって、
ポリアニオンおよび水性媒体を含む液の中で、共役系導電性重合体を得るための単量体化合物を重合して、共役系導電性重合体を含む分散液(1)を得ると共に、前記分散液(1)に分散処理を施して、前記共役系導電性重合体を含有する分散液(2)を得る工程(A)、
前記分散液(2)を、表面に誘電体被膜を有する弁作用金属からなる多孔性陽極体に付着させる工程(B)、および
前記多孔性陽極体に付着した前記分散液(2)から前記水性媒体を除去し固体電解質層を形成する工程(C)
を有し、
前記工程(A)において、前記分散処理を一時停止する操作を1回以上、合計1〜6000分行い、1回の一時停止時間は1〜300分である、
固体電解コンデンサの製造方法。That is, the present invention relates to a method for producing a solid electrolytic capacitor according to the following [1] to [15], a method for producing a solid electrolytic capacitor, and a method for producing a dispersion liquid containing the conjugated conductive polymer according to the following [16].
[1]
A method for manufacturing a solid electrolytic capacitor having a porous anode made of a valve acting metal having a dielectric film on its surface and a solid electrolyte layer provided on the surface of the dielectric film.
A monomer compound for obtaining a conjugated conductive polymer is polymerized in a liquid containing a polyanion and an aqueous medium to obtain a dispersion liquid (1) containing the conjugated conductive polymer, and the dispersion liquid is obtained. A step (A) of subjecting (1) to a dispersion treatment to obtain a dispersion liquid (2) containing the conjugated conductive polymer.
The step (B) of adhering the dispersion liquid (2) to a porous anode made of a valve acting metal having a dielectric film on the surface, and the aqueous dispersion liquid (2) adhering to the porous anode body. Step of removing the medium to form a solid electrolyte layer (C)
Have,
In the step (A), the operation of suspending the dispersion processing is performed once or more for a total of 1 to 6000 minutes, and the suspension time of one time is 1 to 300 minutes.
Manufacturing method of solid electrolytic capacitors.
[2]
前記水性媒体にポリアニオンにより保護コロイド化されたシード粒子が分散している、前記[1]の固体電解コンデンサの製造方法。[2]
The method for producing a solid electrolytic capacitor according to the above [1], wherein seed particles protected and colloidalized by polyanions are dispersed in the aqueous medium.
[3]
前記分散処理を一時停止する操作を2〜20回行う、前記[1]または[2]の固体電解コンデンサの製造方法。[3]
The method for manufacturing a solid electrolytic capacitor according to the above [1] or [2], wherein the operation of suspending the dispersion processing is performed 2 to 20 times.
[4]
前記分散処理を一時停止する時間が合計で6〜2250分である、前記[1]〜[3]のいずれかの固体電解コンデンサの製造方法。[4]
The method for manufacturing a solid electrolytic capacitor according to any one of [1] to [3], wherein the time for suspending the dispersion processing is 6 to 2250 minutes in total.
[5]
前記一時停止後の分散液(1)の粘度が、一時停止前の粘度に比べて1.05〜100.0倍である、前記[1]〜[4]のいずれかの固体電解コンデンサの製造方法。[5]
Production of the solid electrolytic capacitor according to any one of [1] to [4], wherein the viscosity of the dispersion liquid (1) after the suspension is 1.05 to 100.0 times the viscosity before the suspension. Method.
[6]
前記工程(A)において前記分散液(1)に塩化合物を添加する、前記[1]〜[5]のいずれかの固体電解コンデンサの製造方法。[6]
The method for producing a solid electrolytic capacitor according to any one of [1] to [5], wherein a salt compound is added to the dispersion liquid (1) in the step (A).
[7]
前記シード粒子がエチレン性不飽和単量体の重合体の粒子である前記[2]〜[6]のいずれかの固体電解コンデンサの製造方法。[7]
The method for producing a solid electrolytic capacitor according to any one of [2] to [6], wherein the seed particles are particles of a polymer of an ethylenically unsaturated monomer.
[8]
前記工程(A)において前記分散処理が超音波照射による分散処理を含む前記[1]〜[7]のいずれかの固体電解コンデンサの製造方法。[8]
The method for producing a solid electrolytic capacitor according to any one of [1] to [7], wherein in the step (A), the dispersion treatment includes a dispersion treatment by ultrasonic irradiation.
[9]
前記工程(A)において前記分散処理が高圧ホモジナイザーによる分散処理を含む前記[1]〜[8]のいずれかの固体電解コンデンサの製造方法。[9]
The method for producing a solid electrolytic capacitor according to any one of [1] to [8], wherein the dispersion treatment in the step (A) includes a dispersion treatment by a high-voltage homogenizer.
[10]
前記単量体化合物が、ピロール化合物、アニリン化合物、及びチオフェン化合物からなる群から選ばれる少なくとも1種である前記[1]〜[9]のいずれかの固体電解コンデンサの製造方法。[10]
The method for producing a solid electrolytic capacitor according to any one of [1] to [9] above, wherein the monomer compound is at least one selected from the group consisting of a pyrrole compound, an aniline compound, and a thiophene compound.
[11]
前記単量体化合物が、下記式(1)[11]
The monomer compound has the following formula (1).
R1及びR2は、R1とR2とが互いに結合して、置換基を有してもよい置換基以外の部分の炭素数が3〜10の脂環、置換基を有してもよい置換基以外の部分の炭素数が6〜10の芳香環、置換基を有してもよい置換基以外の部分の炭素数が2〜10の酸素原子含有複素環、置換基を有してもよい置換基以外の部分の炭素数が2〜10のイオウ原子含有複素環、若しくは置換基を有してもよい置換基以外の部分の炭素数が2〜10のイオウ原子及び酸素原子含有複素環を表す。)
で示される化合物である前記[1]〜[10]のいずれかの固体電解コンデンサの製造方法。
The method for producing a solid electrolytic capacitor according to any one of the above [1] to [10], which is a compound represented by.
[12]
前記ポリアニオンが、スルホ基およびスルホ基の塩からなる基の少なくとも一方を有するポリマーである前記[1]〜[11]のいずれかの固体電解コンデンサの製造方法。[12]
The method for producing a solid electrolytic capacitor according to any one of [1] to [11], wherein the polyanion is a polymer having at least one of a group consisting of a sulfo group and a salt of a sulfo group.
[13]
前記ポリアニオンが、前記ポリアニオン中のアニオン性基の割合が前記単量体化合物1モルに対し0.25〜30.00モルとなる量で使用される前記[1]〜[12]のいずれかの固体電解コンデンサの製造方法。[13]
Any of the above [1] to [12], wherein the polyanion is used in an amount such that the ratio of the anionic group in the polyanion is 0.25 to 30.00 mol with respect to 1 mol of the monomer compound. A method for manufacturing a solid electrolytic capacitor.
[14]
前記工程(A)において、前記重合がペルオキソ二硫酸及びその塩から選ばれる少なくとも1種の酸化剤を用いて行われる前記[1]〜[13]のいずれかの固体電解コンデンサの製造方法。[14]
The method for producing a solid electrolytic capacitor according to any one of [1] to [13], wherein in the step (A), the polymerization is carried out using at least one oxidizing agent selected from peroxodisulfuric acid and a salt thereof.
[15]
前記[1]〜[14]のいずれかの製造方法により得られた固体電解コンデンサ。
[16]
ポリアニオンおよび水性媒体を含む液の中で、共役系導電性重合体を得るための単量体化合物を重合して、共役系導電性重合体を含む分散液(1)を得ると共に、前記分散液(1)に分散処理を施して、前記共役系導電性重合体を含有する分散液(2)を得る工程(A)を有し、
前記工程(A)において、前記分散処理を一時停止する操作を1回以上、合計1〜6000分行い、1回の一時停止時間は1〜300分である
共役系導電性重合体を含有する分散液(2)の製造方法。[15]
A solid electrolytic capacitor obtained by the production method according to any one of [1] to [14].
[16]
A monomer compound for obtaining a conjugated conductive polymer is polymerized in a liquid containing a polyanion and an aqueous medium to obtain a dispersion liquid (1) containing the conjugated conductive polymer, and the dispersion liquid is obtained. It has a step (A) of subjecting (1) to a dispersion treatment to obtain a dispersion liquid (2) containing the conjugated conductive polymer.
In the step (A), the operation of suspending the dispersion treatment is performed once or more for a total of 1 to 6000 minutes, and the suspension time of each time is 1 to 300 minutes. Dispersion containing a conjugated conductive polymer Method for producing liquid (2).
本発明の固体電解コンデンサの製造方法によれば、容量発現率(静電容量)が高く、かつ等価直列抵抗(ESR)が低い固体電解コンデンサを製造することができる。
本発明の固体電解コンデンサは、容量発現率(静電容量)が高く、かつ等価直列抵抗(ESR)が低い。
さらに本発明の分散液の製造方法によれば、容量発現率(静電容量)が高く、かつ等価直列抵抗(ESR)が低い固体電解コンデンサの製造に有用な、共役系導電性重合体を含有する分散液を製造することができる。According to the method for producing a solid electrolytic capacitor of the present invention, a solid electrolytic capacitor having a high capacitance expression rate (capacitance) and a low equivalent series resistance (ESR) can be produced.
The solid electrolytic capacitor of the present invention has a high capacitance expression rate (capacitance) and a low equivalent series resistance (ESR).
Further, according to the method for producing a dispersion liquid of the present invention, it contains a conjugated conductive polymer useful for producing a solid electrolytic capacitor having a high capacitance expression rate (capacitance) and a low equivalent series resistance (ESR). It is possible to produce a dispersion liquid to be used.
本発明の固体電解コンデンサの製造方法は、
表面に誘電体被膜を有する弁作用金属からなる多孔性陽極体と、前記誘電体被膜の表面に設けられた固体電解質層とを有する固体電解コンデンサの製造方法であって、
ポリアニオンおよび水性媒体を含む液の中で、共役系導電性重合体を得るための単量体化合物を重合して、共役系導電性重合体を含む分散液(1)を得ると共に、前記分散液(1)に分散処理を施して、前記共役系導電性重合体を含有する分散液(2)を得る工程(A)、
前記分散液(2)を、表面に誘電体被膜を有する弁作用金属からなる多孔性陽極体に付着させる工程(B)、および
前記多孔性陽極体に付着した前記分散液(2)から前記水性媒体を除去し固体電解質層を形成する工程(C)
を有し、
前記工程(A)において、前記分散処理を一時停止する操作を1回以上、合計1〜6000分行い、1回の停止時間は1〜300分であることを特徴としている。ただし、各回の停止時間は互いに同一であっても異なっていてもよい。The method for manufacturing a solid electrolytic capacitor of the present invention is
A method for manufacturing a solid electrolytic capacitor having a porous anode made of a valve acting metal having a dielectric film on its surface and a solid electrolyte layer provided on the surface of the dielectric film.
A monomer compound for obtaining a conjugated conductive polymer is polymerized in a liquid containing a polyanion and an aqueous medium to obtain a dispersion liquid (1) containing the conjugated conductive polymer, and the dispersion liquid is obtained. A step (A) of subjecting (1) to a dispersion treatment to obtain a dispersion liquid (2) containing the conjugated conductive polymer.
The step (B) of adhering the dispersion liquid (2) to a porous anode made of a valve acting metal having a dielectric film on the surface, and the aqueous dispersion liquid (2) adhering to the porous anode body. Step of removing the medium to form a solid electrolyte layer (C)
Have,
The step (A) is characterized in that the operation of suspending the dispersion processing is performed once or more for a total of 1 to 6000 minutes, and the stop time of each operation is 1 to 300 minutes. However, the stop time of each time may be the same or different from each other.
本明細書においては、共役系導電性重合体を得るための単量体化合物を1種単独で重合して得られる重合体、および複数種の前記単量体化合物を共重合して得られる共重合体を合わせて「共役系導電性重合体」と言う。 In the present specification, a polymer obtained by polymerizing a monomer compound for obtaining a conjugated conductive polymer alone, and a polymer obtained by copolymerizing a plurality of the above-mentioned monomer compounds. The polymers are collectively referred to as "conjugated conductive polymer".
本明細書において、ポリアニオンがシード粒子の表面に配位して保護コロイドを形成した状態の粒子を「ポリアニオンにより保護コロイド化されたシード粒子」と言う。なお、ポリアニオンは、アニオン性基を2個以上有する重合体を意味する。
本明細書において、「(メタ)アクリル」は、アクリルまたはメタクリルを意味し、また、「(メタ)アクリレート」は、アクリレートまたはメタクリレートを意味する。In the present specification, particles in a state in which polyanions are coordinated on the surface of seed particles to form protective colloids are referred to as “seed particles protected colloidalized by polyanions”. The polyanion means a polymer having two or more anionic groups.
As used herein, "(meth) acrylic" means acrylic or methacrylic, and "(meth) acrylate" means acrylate or methacrylate.
<共役系導電性重合体を含有する分散液(2)を得る工程(A)>
(共役系導電性重合体を含む分散液(1)の調製)
共役系導電性重合体を含む分散液(1)を得る工程は、ポリアニオンおよび水性媒体を含む液の中で上記単量体化合物を重合して行われる。この液のより具体的な態様としては、
(i)単量体化合物、ポリアニオンおよび水性媒体を含む液、および
(ii)単量体化合物、ポリアニオンにより保護コロイド化されたシード粒子および水性媒体を含む液
が挙げられる。液(ii)には、さらにポリアニオン(シード粒子の保護コロイド化に用いられるポリアニオンとは別に添加されるポリアニオン。以下「遊離ポリアニオン」と記載する場合もある。)が含まれていてもよい。<Step (A) of obtaining a dispersion liquid (2) containing a conjugated conductive polymer>
(Preparation of dispersion liquid (1) containing conjugated conductive polymer)
The step of obtaining the dispersion liquid (1) containing the conjugated conductive polymer is carried out by polymerizing the above-mentioned monomer compound in a liquid containing a polyanion and an aqueous medium. As a more specific embodiment of this liquid,
Examples include (i) a liquid containing a monomeric compound, a polyanion and an aqueous medium, and (ii) a liquid containing a monomeric compound, seed particles protected and colloidalized by the polyanion, and an aqueous medium. The liquid (ii) may further contain a polyanion (a polyanion added separately from the polyanion used for protective colloidalization of seed particles; hereinafter may be referred to as “free polyanion”).
共役系導電性重合体を含む分散液(1)は、共役系導電性重合体とポリアニオンとの複合体、および共役系導電性重合体とポリアニオンにより保護コロイド化されたシード粒子との複合体から選択される少なくとも一つの複合体が水性媒体中に分散した分散液である。本工程において、ポリアニオンは共役系導電性重合体にドープされることで複合体を形成すると考えられる。 The dispersion liquid (1) containing the conjugated conductive polymer is composed of a composite of the conjugated conductive polymer and a polyanion, and a composite of the conjugated conductive polymer and seed particles protected and colloidalized by the polyanion. A dispersion in which at least one selected complex is dispersed in an aqueous medium. In this step, it is considered that the polyanion is doped with the conjugated conductive polymer to form a complex.
[単量体化合物]
前記共役系導電性重合体の構成単位を誘導する単量体化合物は、ピロール化合物(すなわち、置換基を有してもよいピロール)、アニリン化合物(すなわち、置換基を有してもよいアニリン)、及びチオフェン化合物(すなわち、置換基を有してもよいチオフェン)から選ばれる1種以上であることが好ましい。置換基としては、例えば炭素数1〜18のアルキル基、炭素数6〜10のアリール基、炭素数5〜10のヘテロアリール基、炭素数1〜18のアルコキシ基、炭素数1〜18のアルキルチオ基、カルボキシ基、水酸基、ハロゲン原子及びシアノ基が挙げられる。なお、上記アルキル基、アリール基、ヘテロアリール基、アルコキシ基及びアルキルチオ基は、カルボキシ基、水酸基、ハロゲン原子およびシアノ基から選ばれる1種以上で置換されていてもよい。また、2つ以上の前記置換基が縮合して環を形成していてもよい。[Polymer compound]
The monomer compound for inducing the constituent unit of the conjugated conductive polymer is a pyrrole compound (that is, pyrrole which may have a substituent) and an aniline compound (that is, an aniline which may have a substituent). , And one or more selected from thiophene compounds (ie, thiophene which may have a substituent). Examples of the substituent include an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heteroaryl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an alkylthio having 1 to 18 carbon atoms. Examples include groups, carboxy groups, hydroxyl groups, halogen atoms and cyano groups. The alkyl group, aryl group, heteroaryl group, alkoxy group and alkylthio group may be substituted with one or more selected from a carboxy group, a hydroxyl group, a halogen atom and a cyano group. Further, two or more of the substituents may be condensed to form a ring.
上記単量体化合物の具体例としては、前記ピロール化合物である、ピロール、N−メチルピロール、3−メチルピロール、3−エチルピロール、3−n−プロピルピロール、3−ブチルピロール、3−オクチルピロール、3−デシルピロール、3−ドデシルピロール、3,4−ジメチルピロール、3,4−ジブチルピロール、3−カルボキシルピロール、3−メチル−4−カルボキシルピロール、3−メチル−4−カルボキシエチルピロール、3−メチル−4−カルボキシブチルピロール、3−ヒドロキシピロール、3−メトキシピロール、3−エトキシピロール、3−ブトキシピロール、3−ヘキシルオキシピロール、3−メチル−4−ヘキシルオキシピロール、3−メチル−4−ヘキシルオキシピロール;
前記アニリン化合物である、アニリン、2−メチルアニリン、3−イソブチルアニリン、2−アニリンスルホン酸、3−アニリンスルホン酸;
前記チオフェン化合物である、チオフェン、3−メチルチオフェン、3−エチルチオフェン、3−プロピルチオフェン、3−ブチルチオフェン、3−ヘキシルチオフェン、3−ヘプチルチオフェン、3−オクチルチオフェン、3−デシルチオフェン、3−ドデシルチオフェン、3−オクタデシルチオフェン、3−ブロモチオフェン、3−クロロチオフェン、3−ヨードチオフェン、3−シアノチオフェン、3−フェニルチオフェン、3,4−ジメチルチオフェン、3,4−ジブチルチオフェン、3−ヒドロキシチオフェン、3−メトキシチオフェン、3−エトキシチオフェン、3−ブトキシチオフェン、3−ヘキシルオキシチオフェン、3−ヘプチルオキシチオフェン、3−オクチルオキシチオフェン、3−デシルオキシチオフェン、3−ドデシルオキシチオフェン、3−オクタデシルオキシチオフェン、3,4−ジヒドロキシチオフェン、3,4−ジメトキシチオフェン、3,4−ジエトキシチオフェン、3,4−ジプロポキシチオフェン、3,4−ジブトキシチオフェン、3,4−ジヘキシルオキシチオフェン、3,4−ジヘプチルオキシチオフェン、3,4−ジオクチルオキシチオフェン、3,4−ジデシルオキシチオフェン、3,4−ジドデシルオキシチオフェン、3,4−エチレンジオキシチオフェン、3,4−プロピレンジオキシチオフェン、3,4−ブチレンジオキシチオフェン、3−メチル−4−メトキシチオフェン、3−メチル−4−エトキシチオフェン、3−カルボキシチオフェン、3−メチル−4−カルボキシチオフェン、3−メチル−4−カルボキシエチルチオフェン、3−メチル−4−カルボキシブチルチオフェン、3,4−エチレンオキシチアチオフェン;
が挙げられる。Specific examples of the above-mentioned monomer compound include the pyrrole compounds, pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, and 3-octylpyrrole. , 3-decylpyrrole, 3-dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl-4-carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3 -Methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, 3-methyl-4 -Hexyloxypyrrole;
The aniline compounds, aniline, 2-methylaniline, 3-isobutylaniline, 2-aniline sulfonic acid, 3-aniline sulfonic acid;
The thiophene compounds, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3- Dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxy Thiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyl Oxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3 , 4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylene dioxy Thiophene, 3,4-butylenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxy Ethylthiophene, 3-methyl-4-carboxybutylthiophene, 3,4-ethyleneoxythithiophene;
Can be mentioned.
前記単量体化合物は、1種単独でまたは2種以上を組み合わせて用いることができる。
前記化合物の中でも、導電性が高い共役系導電性重合体を得る観点からは、ピロール、N−メチルピロール、チオフェン、3−メチルチオフェン、3−メトキシチオフェン及び3,4−エチレンジオキシチオフェンが好ましい。The monomer compound may be used alone or in combination of two or more.
Among the above compounds, pyrrole, N-methylpyrrole, thiophene, 3-methylthiophene, 3-methoxythiophene and 3,4-ethylenedioxythiophene are preferable from the viewpoint of obtaining a conjugated conductive polymer having high conductivity. ..
前記単量体化合物には、上記の化合物の中でも下記式(1)で示される化合物が含まれることが好ましく、下記式(2)で示される化合物が含まれることがより好ましく、3,4−エチレンジオキシチオフェンが含まれることがさらに好ましい。 Among the above compounds, the monomer compound preferably contains a compound represented by the following formula (1), more preferably contains a compound represented by the following formula (2), 3,4-. More preferably, it contains ethylenedioxythiophene.
上記式(1)中、R1及びR2は、各々独立して、水素原子、水酸基、置換基を有してもよい炭素数(置換基の炭素数は含まない。以下も同様である。)1〜18のアルキル基、置換基を有してもよい炭素数1〜18のアルコキシ基、若しくは置換基を有してもよい炭素数1〜18のアルキルチオ基を表す。R1とR2とは互いに結合して環を形成した、置換基を有してもよい炭素数3〜10の脂環、置換基を有してもよい炭素数6〜10の芳香環、置換基を有してもよい炭素数2〜10の酸素原子含有複素環、置換基を有してもよい炭素数2〜10のイオウ原子含有複素環、若しくは置換基を有してもよい炭素数2〜10のイオウ原子及び酸素原子含有複素環を表す。「R1とR2とが互いに結合して環を形成した」とは、「R1とR2とが互いに結合し、式(1)のチオフェン骨格中の2つの炭素原子と共に環を形成した」ことを意味し、R1とR2とが互いに結合して形成された環の炭素数には、チオフェン骨格中の炭素原子2つが含まれる。In the above formula (1), R 1 and R 2 each independently have a hydrogen atom, a hydroxyl group, and a carbon number which may have a substituent (the carbon number of the substituent is not included. The same applies hereinafter. ) Represents an alkyl group of 1 to 18, an alkoxy group having 1 to 18 carbon atoms which may have a substituent, or an alkylthio group having 1 to 18 carbon atoms which may have a substituent. R 1 and R 2 are bonded to each other to form a ring, an alicyclic ring having 3 to 10 carbon atoms which may have a substituent, and an aromatic ring having 6 to 10 carbon atoms which may have a substituent. An oxygen atom-containing heterocycle having 2 to 10 carbon atoms which may have a substituent, a sulfur atom-containing heterocycle having 2 to 10 carbon atoms which may have a substituent, or a carbon which may have a substituent. It represents a heterocycle containing sulfur atoms and oxygen atoms of the number 2 to 10. "R 1 and R 2 were bonded to each other to form a ring" means that "R 1 and R 2 were bonded to each other to form a ring together with two carbon atoms in the thiophene skeleton of the formula (1)." The number of carbon atoms in the ring formed by bonding R 1 and R 2 to each other includes two carbon atoms in the thiophene skeleton.
置換基としては、例えば炭素数6〜10のアリール基、炭素数5〜10のヘテロアリール基、炭素数1〜18のアルコキシ基、炭素数1〜18のアルキルチオ基、カルボキシ基、水酸基、ハロゲン原子及びシアノ基が挙げられる。なお、上記アルキル基、アリール基、ヘテロアリール基、アルコキシ基及びアルキルチオ基は、カルボキシ基、水酸基、ハロゲン原子またはシアノ基で置換されていてもよい。また2つ以上の置換基が縮合して環を形成していてもよい。 Examples of the substituent include an aryl group having 6 to 10 carbon atoms, a heteroaryl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a carboxy group, a hydroxyl group, and a halogen atom. And cyano groups. The alkyl group, aryl group, heteroaryl group, alkoxy group and alkylthio group may be substituted with a carboxy group, a hydroxyl group, a halogen atom or a cyano group. Further, two or more substituents may be condensed to form a ring.
上記酸素原子含有複素環としては、オキシラン環、オキセタン環、フラン環、ヒドロフラン環、ピラン環、ピロン環、ジオキサン環、トリオキサン環等が挙げられる。
上記イオウ原子含有複素環としては、チイラン環、チエタン環、チオフェン環、チアン環、チオピラン環、チオピリリウム環、ベンゾチオピラン環、ジチアン環、ジチオラン環、トリチアン環等が挙げられる。Examples of the oxygen atom-containing heterocycle include an oxylan ring, an oxetane ring, a furan ring, a hydrofuran ring, a pyran ring, a pyrone ring, a dioxane ring, and a trioxane ring.
Examples of the sulfur atom-containing heterocycle include a thielan ring, a thietan ring, a thiophene ring, a thiane ring, a thiopyran ring, a thiopyrylium ring, a benzothiopyran ring, a dithiolane ring, a dithiolane ring, and a trithian ring.
上記イオウ原子及び酸素原子含有複素環としては、オキサチオラン環、オキサチアン環等が挙げられる。
式(2)中、R3及びR4は、各々独立して、水素原子または置換基を有してもよい炭素数1〜4のアルキル基を表し、または、R3とR4とが互いに結合して環を形成した、置換基を有してもよい炭素数3〜6の酸素原子含有複素環を表す。Examples of the sulfur atom- and oxygen atom-containing heterocycles include an oxathiorane ring and an oxatian ring.
In formula (2), R 3 and R 4 each independently represent an alkyl group having 1 to 4 carbon atoms which may have a hydrogen atom or a substituent, or R 3 and R 4 are mutually exclusive. It represents an oxygen atom-containing heterocycle having 3 to 6 carbon atoms, which may have a substituent and is bonded to form a ring.
R3及びR4は、好ましくはR3とR4とが互いに結合して環を形成した、置換基を有してもよい炭素数3〜6の酸素原子含有複素環である。「R3とR4とが互いに結合して環を形成した」とは、「R3とR4とが互いに結合し、隣接する2つの酸素原子、および式(2)のチオフェン骨格中の2つの炭素原子と共に環を形成した」ことを意味し、R3とR4とが互いに結合して形成された環の炭素数には、チオフェン骨格中の炭素原子2つが含まれる。R 3 and R 4 are preferably oxygen atom-containing heterocycles having 3 to 6 carbon atoms which may have a substituent and which R 3 and R 4 are bonded to each other to form a ring. "R 3 and R 4 bonded to each other to form a ring" means that "R 3 and R 4 bonded to each other, two adjacent oxygen atoms, and 2 in the thiophene skeleton of formula (2)." It means that "a ring was formed with one carbon atom", and the carbon number of the ring formed by bonding R 3 and R 4 to each other includes two carbon atoms in the thiophene skeleton.
上記酸素原子含有複素環としては、ジオキサン環、トリオキサン環等が挙げられ、好ましくはジオキサン環である。置換基としては、例えば炭素数1〜18のアルキル基、炭素数6〜10のアリール基、炭素数5〜10のヘテロアリール基、炭素数1〜18のアルコキシ基、炭素数1〜18のアルキルチオ基、カルボキシ基、水酸基、ハロゲン原子及びシアノ基が挙げられる。なお、上記アルキル基、アリール基、ヘテロアリール基、アルコキシ基及びアルキルチオ基は、カルボキシ基、水酸基、ハロゲン原子またはシアノ基で置換されていてもよい。また2つ以上の置換基が縮合して環を形成していてもよい。 Examples of the oxygen atom-containing heterocycle include a dioxane ring, a trioxane ring, and the like, and a dioxane ring is preferable. Examples of the substituent include an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heteroaryl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an alkylthio having 1 to 18 carbon atoms. Examples include groups, carboxy groups, hydroxyl groups, halogen atoms and cyano groups. The alkyl group, aryl group, heteroaryl group, alkoxy group and alkylthio group may be substituted with a carboxy group, a hydroxyl group, a halogen atom or a cyano group. Further, two or more substituents may be condensed to form a ring.
[共役系導電性重合体]
前記共役系導電性重合体は、主鎖にπ共役系を有する有機高分子化合物であれば特に限定されるものではない。共役系導電性重合体としては、ポリピロール類、ポリチオフェン類、ポリイソチアナフテン類、ポリアセチレン類、ポリフェニレン類、ポリフェニレンビニレン類、ポリアニリン類、ポリアセン類、ポリチオフェンビニレン類、及び重合体のモノマー単位を2種以上含む共重合体等が挙げられる。[Conjugated conductive polymer]
The conjugated conductive polymer is not particularly limited as long as it is an organic polymer compound having a π-conjugated system in the main chain. As the conjugated conductive polymer, there are two types of monomer units of polypyrroles, polythiophenes, polyisothianaftens, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and polymers. Examples thereof include copolymers containing the above.
これらの共役系導電性重合体の中でも、導電性が高い点から、ポリピロール、ポリ(N−メチルピロール)、ポリチオフェン、ポリ(3−メチルチオフェン)、ポリ(3−メトキシチオフェン)及びポリ(3,4−エチレンジオキシチオフェン)が好ましい。特に導電性がより高く、耐熱性にも優れていることから、ポリ(3,4−エチレンジオキシチオフェン)(PEDOT)がより好ましい。 Among these conjugated conductive polymers, polypyrrole, poly (N-methylpyrrole), polythiophene, poly (3-methylthiophene), poly (3-methoxythiophene) and poly (3,) are high in conductivity. 4-ethylenedioxythiophene) is preferred. In particular, poly (3,4-ethylenedioxythiophene) (PEDOT) is more preferable because it has higher conductivity and excellent heat resistance.
[ポリアニオン]
前記ポリアニオンは、アニオン性基を有するモノマー単位を2つ以上有する重合体であり、シード粒子の表面に配位して保護コロイドを形成し、かつ、共役系導電性重合体へのドーパントとして機能する。[Polyanion]
The polyanion is a polymer having two or more monomer units having an anionic group, coordinates on the surface of seed particles to form a protective colloid, and functions as a dopant for a conjugated conductive polymer. ..
アニオン性基としては、例えば、スルホ基またはその塩からなる基(スルホ基の水素原子を金属原子等に置換してなる基。たとえばSO3Na、SO3K、SO3(NH4)。)、リン酸基またはその塩からなる基(リン酸基の水素原子を金属原子等に置換してなる基。たとえばPO4Na2、PO4NaH、PO4K2、PO4KH、PO4(NH4)2、PO4(NH4)H。)、一置換リン酸エステル基、カルボキシル基またはその塩からなる基(カルボキシル基の水素原子を金属原子等に置換してなる基。たとえばCOONa、COOK、COO(NH4)。)、一置換硫酸エステル基が挙げられる。これらの中でも、強酸性基が好ましく、スルホ基またはその塩からなる基、及びリン酸基またはその塩からなる基がより好ましく、スルホ基またはその塩からなる基がさらに好ましい。Examples of the anionic group include a sulfo group or a group consisting of a salt thereof (a group formed by substituting a hydrogen atom of a sulfo group with a metal atom or the like. For example, SO 3 Na, SO 3 K, SO 3 (NH 4 )). , A group consisting of a phosphoric acid group or a salt thereof (a group formed by substituting a hydrogen atom of a phosphoric acid group with a metal atom, etc. For example, PO 4 Na 2 , PO 4 NaH, PO 4 K 2 , PO 4 KH, PO 4 ( NH 4 ) 2 , PO 4 (NH 4 ) H.), monosubstituted phosphate group, carboxyl group or a group consisting of a salt thereof (a group formed by substituting a hydrogen atom of a carboxyl group with a metal atom, for example, COONa, COOK, COO (NH 4 ).), Monosubstituted sulfate group. Among these, a strongly acidic group is preferable, a group composed of a sulfo group or a salt thereof, a group composed of a phosphoric acid group or a salt thereof is more preferable, and a group composed of a sulfo group or a salt thereof is further preferable.
アニオン性基は、重合体の主鎖に直接結合していても、側鎖に結合していてもよい。アニオン性基が側鎖に結合している場合、ドープ効果がより顕著となることから、側鎖の末端に結合していることが好ましい。 The anionic group may be directly attached to the main chain of the polymer or may be attached to the side chain. When the anionic group is attached to the side chain, the doping effect becomes more remarkable, so that it is preferably attached to the end of the side chain.
ポリアニオンは、アニオン性基以外の置換基及び/または結合構造を有してもよい。置換基としては、アルキル基、水酸基、アルコキシ基、シアノ基、フェニル基、ヒドロキシフェニル基、ハロゲノ基、アルケニル基、アミノ基、オキシカルボニル基、カルボニル基等が挙げられる。結合構造としては、エステル結合、イミド結合、アミド結合等が挙げられる。これらの中でアルキル基、水酸基、シアノ基、ヒドロキシフェニル基、オキシカルボニル基が好ましく、アルキル基、水酸基、シアノ基がより好ましい。置換基及び/または結合構造はポリマー主鎖に直接結合していてもよいし、側鎖に結合していてもよい。側鎖に置換基が結合している場合にそれぞれの置換基の作用効果を示すため、置換基は側鎖の末端に結合していることが好ましい。 The polyanion may have a substituent and / or a bonded structure other than the anionic group. Examples of the substituent include an alkyl group, a hydroxyl group, an alkoxy group, a cyano group, a phenyl group, a hydroxyphenyl group, a halogeno group, an alkenyl group, an amino group, an oxycarbonyl group and a carbonyl group. Examples of the bond structure include an ester bond, an imide bond, and an amide bond. Among these, an alkyl group, a hydroxyl group, a cyano group, a hydroxyphenyl group and an oxycarbonyl group are preferable, and an alkyl group, a hydroxyl group and a cyano group are more preferable. The substituent and / or bond structure may be directly attached to the polymer main chain or may be attached to the side chain. When a substituent is attached to the side chain, the effect of each substituent is exhibited. Therefore, it is preferable that the substituent is attached to the end of the side chain.
ポリアニオン中に置換し得るアルキル基は、水性媒体への溶解性及び分散性、共役系導電性重合体との相溶性及び分散性等を高くする作用が期待できる。アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、t−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の鎖状アルキル基;シクロプロピル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基が挙げられる。水性媒体への溶解性、共役系導電性重合体への分散性、立体障害等を考慮すると、炭素数1〜12のアルキル基がより好ましい。 Alkyl groups that can be substituted in polyanions can be expected to have an effect of increasing solubility and dispersibility in aqueous media, compatibility and dispersibility with conjugated conductive polymers, and the like. Alkyl groups include methyl group, ethyl group, propyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and other chain alkyl groups; cyclopropyl group, Cycloalkyl groups such as cyclopentyl group and cyclohexyl group can be mentioned. Considering the solubility in an aqueous medium, the dispersibility in a conjugated conductive polymer, the steric hindrance, and the like, an alkyl group having 1 to 12 carbon atoms is more preferable.
ポリアニオン中に置換し得る水酸基は、他の水素原子等との水素結合を形成しやすくし、水性媒体への溶解性、共役系導電性重合体との相溶性、分散性、接着性を高くする作用が期待できる。水酸基は、ポリマー主鎖に結合した炭素数1〜6のアルキル基の末端に結合したものが好ましい。 Hydroxy groups that can be substituted in polyanions facilitate the formation of hydrogen bonds with other hydrogen atoms, etc., and enhance the solubility in aqueous media, compatibility with conjugated conductive polymers, dispersibility, and adhesiveness. Expected to work. The hydroxyl group is preferably bonded to the terminal of an alkyl group having 1 to 6 carbon atoms bonded to the polymer main chain.
ポリアニオン中に置換し得るシアノ基及びヒドロキシフェニル基は、共役系導電性重合体との相溶性、水性媒体への溶解性、耐熱性を高くする作用が期待できる。シアノ基は、ポリマー主鎖に直接結合したもの、ポリマー主鎖に結合した炭素数1〜7のアルキル基の末端に結合したもの、ポリマー主鎖に結合した炭素数2〜7のアルケニル基の末端に結合したものが好ましい。ヒドロキシフェニル基は、4−ヒドロキシフェニル基が好ましい。 The cyano group and hydroxyphenyl group that can be substituted in the polyanion can be expected to have an action of increasing compatibility with a conjugated conductive polymer, solubility in an aqueous medium, and heat resistance. The cyano group is directly bonded to the polymer main chain, bonded to the terminal of an alkyl group having 1 to 7 carbon atoms bonded to the polymer main chain, or the terminal of an alkenyl group having 2 to 7 carbon atoms bonded to the polymer main chain. It is preferably bound to. The hydroxyphenyl group is preferably a 4-hydroxyphenyl group.
ポリアニオン中に置換し得るオキシカルボニル基は、ポリマー主鎖に直接結合した、アルキルオキシカルボニル基、アリールオキシカルボニル基、他の官能基を介在してなるアルキルオキシカルボニル基またはアリールオキシカルボニル基が好ましい。 The oxycarbonyl group that can be substituted in the polyanion is preferably an alkyloxycarbonyl group, an aryloxycarbonyl group, or an alkyloxycarbonyl group or an aryloxycarbonyl group that is directly bonded to the polymer main chain and is formed by interposing another functional group.
ポリアニオンのポリマー主鎖の組成は、特に制限されない。ポリマー主鎖としては、例えば、ポリアルキレン、ポリイミド、ポリアミド、ポリエステル等が挙げられる。これらのうち、合成や入手し易さの観点から、ポリアルキレンが好ましい。 The composition of the polymer main chain of the polyanion is not particularly limited. Examples of the polymer main chain include polyalkylene, polyimide, polyamide, polyester and the like. Of these, polyalkylene is preferable from the viewpoint of synthesis and availability.
ポリアルキレンは、エチレン性不飽和単量体の繰り返し単位で構成されるポリマーである。ポリアルキレンは主鎖に炭素−炭素二重結合を有してもよい。ポリアルキレンとしては、例えば、ポリエチレン、ポリプロピレン、ポリブテン、ポリペンテン、ポリヘキセン、ポリビニルアルコール、ポリビニルフェノール、ポリ(3,3,3−トリフルオロプロピレン)、ポリアクリロニトリル、ポリアクリレート、ポリメタクリレート、ポリスチレン、ポリブタジエン、ポリイソプレン等が挙げられる。 Polyalkylene is a polymer composed of repeating units of ethylenically unsaturated monomers. The polyalkylene may have a carbon-carbon double bond in the main chain. Examples of the polyalkylene include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polymethacrylate, polystyrene, polybutadiene, and poly. Isoprene and the like can be mentioned.
ポリイミドとしては、ピロメリット酸二無水物、ビフェニルテトラカルボン酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、2,2,3,3−テトラカルボキシジフェニルエーテル二無水物、2,2−[4,4'−ジ(ジカルボキシフェニルオキシ)フェニル]プロパン二無水物等の酸無水物とオキシジアニリン、パラフェニレンジアミン、メタフェニレンジアミン、ベンゾフェノンジアミン等のジアミンとの重縮合反応で得られるものが挙げられる。 As the polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2,3,3-tetracarboxydiphenylether dianhydride, 2,2- [4,4 '-Di (dicarboxyphenyloxy) phenyl] Examples thereof include those obtained by a polycondensation reaction between an acid anhydride such as propanedianhydride and a diamine such as oxydianiline, paraphenylenediamine, metaphenylenediamine and benzophenonediamine. ..
ポリアミドとしては、ポリアミド6、ポリアミド6,6、ポリアミド6,10等が挙げられる。
ポリエステルとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等が挙げられる。Examples of the polyamide include
Examples of polyester include polyethylene terephthalate and polybutylene terephthalate.
ポリアニオンとして好適に用いられるスルホ基およびスルホ基の塩からなる基の少なくとも一方を有するポリマーの具体例としては、ポリビニルスルホン酸、ポリスチレンスルホン酸、ポリアリルスルホン酸、ポリアクリル酸エチルスルホン酸、ポリアクリル酸ブチルスルホン酸、ポリ(2−アクリルアミド−2−メチルプロパンスルホン酸)、およびポリイソプレンスルホン酸、ならびにこれらの全部または一部のスルホ基をスルホ基の塩からなる基に置き換えたもの等が挙げられる。これらは単独重合体であってもよいし、2種以上のモノマー単位を含む共重合体であってもよい。これらのうち、導電性付与の点から、ポリスチレンスルホン酸、ポリイソプレンスルホン酸、およびポリアクリル酸エチルスルホン酸、ポリアクリル酸ブチルスルホン酸、ならびにこれらの全部または一部のスルホ基をスルホ基の塩からなる基に置き換えたものが好ましく、ポリスチレンスルホン酸(PSS)、およびポリスチレンスルホン酸の全部または一部のスルホ基をスルホ基の塩からなる基に置き換えたものがより好ましい。 Specific examples of a polymer having at least one of a sulfo group and a group consisting of a salt of the sulfo group, which are preferably used as polyanions, include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, ethyl sulfonic acid polyacrylate, and polyacrylic acid. Acids Butyl sulfonic acid, poly (2-acrylamide-2-methylpropane sulfonic acid), and polyisoprene sulfonic acid, and all or part of these sulfo groups replaced with groups consisting of salts of sulfo groups. Be done. These may be homopolymers or copolymers containing two or more kinds of monomer units. Of these, polystyrene sulfonic acid, polyisoprene sulfonic acid, ethyl sulfonic acid polyacrylate, butyl sulfonic acid polyacrylate, and all or part of these sulfo groups are salts of sulfo groups from the viewpoint of imparting conductivity. It is preferably replaced with a group consisting of a group consisting of, and more preferably a group consisting of a salt of a sulfo group in which all or part of the sulfo group of polystyrene sulfonic acid (PSS) and polystyrene sulfonic acid is replaced.
ポリアニオン、特にスルホ基およびスルホ基の塩からなる基の少なくとも一方を有するポリマーは、単量体化合物の水性媒体中での分散性を向上させ、さらに共役系導電性重合体のドーパントとして機能する。 A polymer having at least one of a polyanion, particularly a group consisting of a sulfo group and a salt of a sulfo group, improves the dispersibility of the monomeric compound in an aqueous medium and further functions as a dopant for a conjugated conductive polymer.
前記ポリアニオンの重量平均分子量は、好ましくは1,000〜1,000,000、より好ましくは5,000〜500,000、さらに好ましくは50,000〜300,000である。重量平均分子量がこの範囲にあると、ポリアニオンの水性媒体への溶解性、ポリアニオンの共役系導電性重合体へのドーピングが良好となる。なお、ここで言う重量平均分子量は、ゲルパーミエーションクロマトグラフィーを用いて、ポリスチレン換算分子量として測定された値である。 The weight average molecular weight of the polyanion is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, and even more preferably 50,000 to 300,000. When the weight average molecular weight is in this range, the solubility of the polyanion in the aqueous medium and the doping of the polyanion into the conjugated conductive polymer are good. The weight average molecular weight referred to here is a value measured as a polystyrene-equivalent molecular weight using gel permeation chromatography.
ポリアニオンは市販品の中から上記特性を有するものを選択してもよいし、または公知の方法により合成したものでもよい。ポリアニオンの合成法は、例えば、特開2005−76016号公報に記載されている。 The polyanion may be a commercially available product having the above-mentioned characteristics, or may be synthesized by a known method. A method for synthesizing a polyanion is described in, for example, Japanese Patent Application Laid-Open No. 2005-76016.
ポリアニオンの使用量、すなわちシード粒子の保護コロイド化に使用されるもの、重合開始前に予め仕込んでおくもの及び重合途上で添加するものを合わせたポリアニオンの総使用量は、ポリアニオン中のアニオン性基が、単量体化合物1モルに対して、好ましくは0.25〜30モル、より好ましくは0.5〜28モル、さらに好ましくは0.8〜25モルとなる量である。 The total amount of polyanions used, that is, those used for protective colloidalization of seed particles, those pre-prepared before the start of polymerization and those added during polymerization, is the total amount of polyanions used in the polyanions. However, the amount is preferably 0.25 to 30 mol, more preferably 0.5 to 28 mol, and further preferably 0.8 to 25 mol with respect to 1 mol of the monomer compound.
また、本工程で製造される共役系導電性重合体100質量部に対するポリアニオンの使用量は、好ましくは10〜30,000質量部、より好ましくは30〜20,000質量部、さらに好ましくは50〜15,000質量部である。
ポリアニオンの使用量が10質量部以上であれば導電性重合体の導電性が適切であり、30,000質量部以下であれば導電性重合体の水性媒体中での分散性が良好である。The amount of the polyanion used with respect to 100 parts by mass of the conjugated conductive polymer produced in this step is preferably 10 to 30,000 parts by mass, more preferably 30 to 20,000 parts by mass, and further preferably 50 to 50 parts by mass. It is 15,000 parts by mass.
When the amount of the polyanion used is 10 parts by mass or more, the conductivity of the conductive polymer is appropriate, and when it is 30,000 parts by mass or less, the dispersibility of the conductive polymer in an aqueous medium is good.
[シード粒子]
本発明に用いられてもよいシード粒子は、水性媒体中でポリアニオンにより保護コロイド化されたポリマー粒子である。シード粒子としては、例えば、1種または2種以上のエチレン性不飽和単量体を構成単位として含む重合体からなるものが好ましい。重合体は、1種単独でも、2種以上の混合物でもよく、また、結晶性または非晶性のいずれでもよい。結晶性の場合は、結晶化度が50%以下であることが好ましい。[Seed particles]
The seed particles that may be used in the present invention are polymer particles that are protected colloidalized with polyanions in an aqueous medium. As the seed particles, for example, those composed of a polymer containing one or more kinds of ethylenically unsaturated monomers as a constituent unit are preferable. The polymer may be one kind alone, a mixture of two or more kinds, and may be either crystalline or amorphous. In the case of crystallinity, the crystallinity is preferably 50% or less.
結晶化度は、示差走査熱量計またはX線回折装置で測定することができる。
エチレン性不飽和単量体は、重合性のエチレン性炭素−炭素二重結合を1個以上有する単量体である。エチレン性不飽和単量体としては、例えば、直鎖状、分岐状または環状のアルキル鎖を有する(メタ)アクリレート;スチレン、α−メチルスチレン等の芳香族ビニル化合物;ビニルピロリドン等の複素環式ビニル化合物;ヒドロキシアルキル(メタ)アクリレート;ジメチルアミノエチルアクリレート等のジアルキルアミノアルキル(メタ)アクリレート;酢酸ビニル、アルカン酸ビニル等のビニルエステル;エチレン、プロピレン、ブチレン、イソブチレン等のモノオレフィン;ブタジエン、イソプレン、クロロプレン等のハロゲン原子を有していてもよい共役ジオレフィン;アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸等のα,β−不飽和モノあるいはジカルボン酸;アクリロニトリル等のシアン化ビニル化合物;アクロレイン、ダイアセトンアクリルアミド等のカルボニル基含有ビニル化合物が挙げられる。これらのエチレン性不飽和単量体は、1種単独でまたは2種以上を組み合わせて使用してもよい。The crystallinity can be measured with a differential scanning calorimeter or an X-ray diffractometer.
The ethylenically unsaturated monomer is a monomer having one or more polymerizable ethylenically carbon-carbon double bonds. Examples of the ethylenically unsaturated monomer include (meth) acrylates having linear, branched or cyclic alkyl chains; aromatic vinyl compounds such as styrene and α-methylstyrene; heterocyclic compounds such as vinylpyrrolidone. Vinyl compounds; hydroxyalkyl (meth) acrylates; dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl acrylate; vinyl esters such as vinyl acetate and vinyl alkanoate; monoolefins such as ethylene, propylene, butylene and isobutylene; butadiene, isoprene , Coupling diolefins that may have halogen atoms such as chloroprene; α, β-unsaturated mono or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid; acrylonitrile and the like. Vinyl cyanide compounds; examples thereof include carbonyl group-containing vinyl compounds such as acrylonitrile and diacetoneacrylamide. These ethylenically unsaturated monomers may be used alone or in combination of two or more.
また、エチレン性不飽和単量体は、架橋性単量体であってもよく、それ自身同士を、または架橋性単量体と活性水素基を持つエチレン性不飽和化合物と組み合わせて架橋させてもよい。架橋した共重合体とすることにより、導電膜の耐水性、耐湿性、耐熱性等を向上させることができる。なお、架橋性単量体とは、エチレン性炭素−炭素二重結合を2個以上有する化合物、またはエチレン性炭素−炭素二重結合を1個以上有し、かつその他の反応性基を1個以上有する化合物を言う。 The ethylenically unsaturated monomer may be a crosslinkable monomer, and is crosslinked with each other or in combination with a crosslinkable monomer and an ethylenically unsaturated compound having an active hydrogen group. May be good. By using a crosslinked copolymer, the water resistance, moisture resistance, heat resistance, etc. of the conductive film can be improved. The crosslinkable monomer is a compound having two or more ethylenic carbon-carbon double bonds, or one or more ethylenic carbon-carbon double bonds and one other reactive group. The compound having the above.
架橋性単量体としては、例えば、グリシジル(メタ)アクリレート等のエポキシ基含有α,β−エチレン性不飽和化合物;ビニルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等の加水分解性アルコキシシリル基含有α,β−エチレン性不飽和化合物;エチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、アリル(メタ)アクリレート、ジビニルベンゼン、ジアリルフタレート等の多官能ビニル化合物等が挙げられる。 Examples of the crosslinkable monomer include epoxy group-containing α, β-ethylenically unsaturated compounds such as glycidyl (meth) acrylate; hydrolyzable alkoxysilyls such as vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane. Group-containing α, β-ethylenically unsaturated compounds; polyfunctional vinyl compounds such as ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate and the like can be mentioned. ..
また、カルボニル基含有α,β−エチレン性不飽和化合物(ケトン基含有のもの)等の架橋性単量体を用いて、ポリヒドラジン化合物(特に、シュウ酸ジヒドラジド、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、ポリアクリル酸ヒドラジド等の2個以上のヒドラジド基を有するもの)と組み合わせて架橋させてもよい。
エチレン性不飽和単量体中の架橋性単量体の含有量は、50質量%以下が好ましく、35質量%以下がより好ましく、25質量%以下がさらに好ましい。Further, using a crosslinkable monomer such as a carbonyl group-containing α, β-ethylenically unsaturated compound (containing a ketone group), a polyhydrazine compound (particularly, oxalic acid dihydrazide, succinate dihydrazide, adipic acid dihydrazide, etc. It may be crosslinked in combination with (having two or more hydrazide groups such as polyacrylic acid hydrazide).
The content of the crosslinkable monomer in the ethylenically unsaturated monomer is preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less.
(ポリアニオンによって保護コロイド化されたシード粒子の製造)
シード粒子は、水性媒体中でポリアニオンによって保護コロイド化される。水性媒体中に分散した保護コロイド化されたシード粒子の分散液は、樹脂エマルジョンとして製造することができる。(Production of seed particles protected and colloidalized by polyanions)
Seed particles are protected colloidalized by polyanions in an aqueous medium. The dispersion of the protective colloidalized seed particles dispersed in the aqueous medium can be produced as a resin emulsion.
樹脂エマルジョンを製造する際のエチレン性不飽和単量体の重合反応は、ラジカル重合反応であり、常圧反応器または耐圧反応器を用い、バッチ式、半連続式、連続式のいずれかの方法で行われる。また、重合時の反応安定性や重合体の均一性の点から、ポリアニオンを水性媒体中に予め溶解させたポリアニオン含有液に、エチレン性不飽和単量体を水性媒体中に溶解、乳化または分散させたエチレン性不飽和単量体溶液を連続的または断続的に添加して、エチレン性不飽和単量体を重合させることが好ましい。 The polymerization reaction of the ethylenically unsaturated monomer in producing a resin emulsion is a radical polymerization reaction, which is a batch type, semi-continuous type, or continuous type using a normal pressure reactor or a pressure resistant reactor. It is done in. Further, from the viewpoint of reaction stability during polymerization and uniformity of the polymer, the ethylenically unsaturated monomer is dissolved, emulsified or dispersed in the aqueous medium in the polyanion-containing solution in which the polyanion is previously dissolved in the aqueous medium. It is preferable to polymerize the ethylenically unsaturated monomer by continuously or intermittently adding the prepared ethylenically unsaturated monomer solution.
反応温度は、重合開始剤の分解温度にもよるが、通常、10〜100℃であり、30〜90℃が一般的である。反応時間は、特に制限されることはなく、各成分の使用量、重合開始剤の種類及び反応温度等に応じて適宜調整すればよい。 The reaction temperature depends on the decomposition temperature of the polymerization initiator, but is usually 10 to 100 ° C, generally 30 to 90 ° C. The reaction time is not particularly limited, and may be appropriately adjusted according to the amount of each component used, the type of polymerization initiator, the reaction temperature, and the like.
ラジカル重合する際、保護コロイドであるポリアニオンがエマルジョン粒子の安定性に寄与するが、必要に応じてアニオン性乳化剤、ノニオン性乳化剤及び反応性乳化剤等の乳化剤や、脂肪族アミン等を重合系内に添加してもよい。乳化剤、脂肪族アミンの種類や使用量は、ポリアニオンの使用量、エチレン性不飽和単量体の組成をはじめとした種々の条件に応じて適宜調節すればよい。 During radical polymerization, polyanions, which are protective colloids, contribute to the stability of emulsion particles. If necessary, emulsifiers such as anionic emulsifiers, nonionic emulsifiers and reactive emulsifiers, and aliphatic amines can be added to the polymerization system. It may be added. The type and amount of the emulsifier and the aliphatic amine may be appropriately adjusted according to various conditions such as the amount of the polyanion used and the composition of the ethylenically unsaturated monomer.
このようなラジカル重合反応に使用する乳化剤としては、例えば、アルキル硫酸エステル塩、アルキルベンゼンスルフォン酸塩、アルキルスルホコハク酸塩、アルキルジフェニルエーテルジスルフォン酸塩、ポリオキシアルキレンアルキル硫酸塩、ポリオキシアルキレンアルキルリン酸エステル等のアニオン性乳化剤、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェノールエーテル、ポリオキシアルキレン脂肪酸エステル、ポリオキシアルキレンソルビタン脂肪酸エステル等のノニオン系界面活性剤が挙げられる。 Examples of the emulsifier used for such a radical polymerization reaction include alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, polyoxyalkylene alkyl sulfate, and polyoxyalkylene alkyl phosphate. Examples thereof include anionic emulsifiers such as esters, and nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene fatty acid esters, and polyoxyalkylene sorbitan fatty acid esters.
脂肪族アミンとしては、オクチルアミン、ラウリルアミン、ミリスチルアミン、ステアリルアミン、オレイルアミン等の1級アミン、ジオクチルアミン、ジラウリルアミン、ジステアリルアミン、ジオレイルアミン等の2級アミン、N,N−ジメチルラウリルアミン、N,N−ジメチルミリスチルアミン、N,N−ジメチルパルミチルアミン、N,N−ジメチルステアリルアミン、N,N−ジメチルベヘニルアミン、N,N−ジメチルオレイルアミン、N−メチルジデシルアミン、N−メチルジオレイルアミン等の3級アミン等が挙げられる。
乳化剤及び脂肪族アミンは、1種単独でまたは2種以上を組み合わせて使用してもよい。
Examples of the aliphatic amine include primary amines such as octylamine, laurylamine, myristylamine, stearylamine and oleylamine, secondary amines such as dioctylamine, dilaurylamine, distearylamine and diorailamine, and N, N-dimethyllauryl. Amine, N, N-dimethylmyristylamine, N, N-dimethylpalmitylamine, N, N-dimethylstearylamine, N , N-dimethylbehenylamine, N, N-dimethyloleylamine, N-methyldidecylamine, N − Tertiary amines such as methyldiorail amines can be mentioned.
The emulsifier and the aliphatic amine may be used alone or in combination of two or more.
また、得られる共役系導電性重合体の特性を損なわない範囲で、上述したエチレン性不飽和単量体の重合反応を行う際に、水性媒体中にポリビニルアルコール、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ポリビニルピロリドン等の水溶性高分子を併存させてもよい。 Further, when the above-mentioned polymerization reaction of the ethylenically unsaturated monomer is carried out within a range that does not impair the characteristics of the obtained conjugated conductive polymer, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, etc. are contained in the aqueous medium. A water-soluble polymer such as hydroxypropyl cellulose or polyvinylpyrrolidone may coexist.
シード粒子の分散液を製造する際に使用される水性媒体としては、水、または水と水溶性溶媒との混合溶媒が挙げられる。混合溶媒中での水溶性溶媒の割合は0〜30質量%が好ましい。水溶性溶媒の割合が30質量%以下であると樹脂エマルジョンの重合反応を安定化させることができる。水溶性溶媒としては、メタノール、エタノール、イソプロピルアルコール等のアルコール類;アセトン等のケトン類;エチレングリコール、プロピレングリコール等のグリコール類;エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル等のエーテル類等が挙げられる。 Examples of the aqueous medium used in producing the dispersion of seed particles include water or a mixed solvent of water and a water-soluble solvent. The ratio of the water-soluble solvent in the mixed solvent is preferably 0 to 30% by mass. When the proportion of the water-soluble solvent is 30% by mass or less, the polymerization reaction of the resin emulsion can be stabilized. Examples of the water-soluble solvent include alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether. ..
ラジカル重合に際して使用される重合開始剤としては、公知慣用のものを使用することができる。重合開始剤としては、例えば、過酸化水素、過硫酸、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物類;ベンゾイルパーオキサイド、t−ブチルハイドロパーオキサイド等の有機過酸化物類;2,2'−アゾビスイソブチロニトリル、4,4'−アゾビス(4−シアノ吉草酸)等のアゾ化合物類が挙げられる。また、必要に応じて、これらの重合開始剤をナトリウムスルホキシレートホルムアルデヒド、アスコルビン酸類、亜硫酸塩類、酒石酸またはその塩類、硫酸鉄(II)等と組み合わせてレドックス重合としてもよい。また、必要に応じて、アルコール類、メルカプタン類等の連鎖移動剤を使用してもよい。 As the polymerization initiator used in the radical polymerization, known and commonly used ones can be used. Examples of the polymerization initiator include inorganic peroxides such as hydrogen peroxide, persulfate, ammonium persulfate, potassium persulfate, and sodium persulfate; and organic peroxides such as benzoyl peroxide and t-butyl hydroperoxide. Includes azo compounds such as 2,2'-azobisisobutyronitrile and 4,4'-azobis (4-cyanovaleric acid). Further, if necessary, these polymerization initiators may be combined with sodium sulfoxylate formaldehyde, ascorbic acids, sulfites, tartaric acid or salts thereof, iron (II) sulfate and the like for redox polymerization. Further, if necessary, a chain transfer agent such as alcohols and mercaptans may be used.
保護コロイド化されたシード粒子の製造時におけるエチレン性不飽和単量体の使用量は、ポリアニオン100質量部に対して、好ましくは10〜100質量部、より好ましくは20〜80質量部、さらに好ましくは30〜70質量部である。エチレン性不飽和単量体の使用量が10質量部以上であれば、共役系導電性重合体に占めるポリアニオンによって保護コロイド化されたシード粒子を含む導電性重合体の割合が適切であり、重合による増粘を抑制できる。100質量部以下であれば、保護コロイド化されたシード粒子の安定性が良好である。 The amount of the ethylenically unsaturated monomer used in the production of the protective colloidalized seed particles is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 100 parts by mass with respect to 100 parts by mass of the polyanion. Is 30 to 70 parts by mass. When the amount of the ethylenically unsaturated monomer used is 10 parts by mass or more, the proportion of the conductive polymer containing the seed particles protected and colloidalized by the polyanion in the conjugated conductive polymer is appropriate, and the polymerization is carried out. It is possible to suppress thickening due to. When it is 100 parts by mass or less, the stability of the protective colloidalized seed particles is good.
保護コロイド化されて、水性媒体中に分散しているシード粒子の粒径のd50(体積基準での50%メジアン径)は、0.01〜10μmであることが好ましく、より好ましくは0.05〜1μmで、さらに好ましくは0.1〜0.8μmである。シード粒子の粒子径分布は、日機装(株)製、マイクロトラックUPA型粒度分布測定装置にて測定できる。水性媒体中に分散しているシード粒子の粒径のd50が0.01μm以上であればシード粒子の分散性が良好であり、10μm以下であれば粒子が沈降しにくい。 The particle size d50 (50% median diameter on a volume basis) of the seed particles that have been protected and colloidalized and dispersed in the aqueous medium is preferably 0.01 to 10 μm, more preferably 0.05. It is ~ 1 μm, more preferably 0.1 to 0.8 μm. The particle size distribution of the seed particles can be measured with a Microtrack UPA type particle size distribution measuring device manufactured by Nikkiso Co., Ltd. When the particle size d50 of the seed particles dispersed in the aqueous medium is 0.01 μm or more, the dispersibility of the seed particles is good, and when it is 10 μm or less, the particles are difficult to settle.
《単量体化合物の重合》
単量体化合物の重合は、当該単量体化合物、ポリアニオンおよび水性媒体を含む液の中で行われる。この液のより具体的な態様としては、
(i)当該単量体化合物、ポリアニオンおよび水性媒体を含む液、および
(ii)当該単量体化合物、ポリアニオンにより保護コロイド化されたシード粒子および水性媒体を含む液
が挙げられる。<< Polymerization of monomeric compounds >>
Polymerization of the monomeric compound is carried out in a liquid containing the monomeric compound, a polyanion and an aqueous medium. As a more specific embodiment of this liquid,
Examples thereof include (i) a liquid containing the monomer compound, the polyanion and an aqueous medium, and (ii) a liquid containing the seed particles and the aqueous medium protected and colloidalized by the monomer compound and the polyanion.
[単量体化合物液]
単量体化合物を上記液中で重合するためには、単量体化合物とポリアニオンとを含む分散液、または単量体化合物とポリアニオンにより保護コロイド化されたシード粒子とを含む分散液(以下、併せて単に「単量体化合物液」と称すことがある。)を調製する。[Polymer compound solution]
In order to polymerize the monomer compound in the above liquid, a dispersion liquid containing the monomer compound and the polyanion, or a dispersion liquid containing the monomer compound and the seed particles protected and colloidalized by the polyanion (hereinafter referred to as At the same time, it may be simply referred to as "monomer compound solution").
上記単量体化合物液は、単量体化合物が溶解、乳化または分散しているものであればよく、そのためには通常、ホモジナイザー等の強力な撹拌装置または超音波照射装置が使用される。たとえば、超音波照射による乳化の場合、超音波照射エネルギーは、均一な単量体化合物液が得られるのであれば特に限定されない。超音波照射は、消費電力5〜500W/L(リットル)、照射時間0.1〜2時間/L(リットル)で行うことが好ましい。 The monomer compound solution may be any one in which the monomer compound is dissolved, emulsified or dispersed, and for that purpose, a powerful stirring device such as a homogenizer or an ultrasonic irradiation device is usually used. For example, in the case of emulsification by ultrasonic irradiation, the ultrasonic irradiation energy is not particularly limited as long as a uniform monomeric compound solution can be obtained. The ultrasonic irradiation is preferably performed with a power consumption of 5 to 500 W / L (liter) and an irradiation time of 0.1 to 2 hours / L (liter).
また、単量体化合物液として単量体化合物とポリアニオンにより保護コロイド化されたシード粒子とを含む分散液を用いる場合には、重合により生成する共役系導電性重合体の凝集を抑える観点から、シード粒子の保護コロイド化に使用されるものと同じポリアニオン(すなわち、遊離ポリアニオン)を単量体化合物液に含有させることが好ましい。このポリアニオン(すなわち、遊離ポリアニオン)は、単量体化合物液に添加し、溶解、乳化または分散させることによって含有させることができる。遊離ポリアニオンを単量体化合物液に含有させる場合、その量は、使用するポリアニオンの総量(すなわち、シード粒子の保護コロイド化に使用されているポリアニオンおよび遊離ポリアニオンの合計量)の5〜99質量%が好ましく、10〜90質量%がより好ましく、20〜80質量%がさらに好ましい。 Further, when a dispersion containing the monomer compound and the seed particles protected and colloidalized by the polyanion is used as the monomer compound solution, from the viewpoint of suppressing the aggregation of the conjugated conductive polymer generated by the polymerization, from the viewpoint of suppressing the aggregation of the conjugated conductive polymer. It is preferred that the monomeric compound solution contain the same polyanions (ie, free polyanions) used for protective colloidalization of seed particles. This polyanion (ie, free polyanion) can be contained by adding to the monomeric compound solution and dissolving, emulsifying or dispersing. When the free polyanion is contained in the monomer compound solution, the amount thereof is 5 to 99% by mass of the total amount of the polyanion used (that is, the total amount of the polyanion and the free polyanion used for the protective colloidalization of the seed particles). Is preferable, 10 to 90% by mass is more preferable, and 20 to 80% by mass is further preferable.
[水性媒体]
単量体化合物の重合に用いられる水性媒体は、共役系導電性重合体とポリアニオンにより保護コロイド化されたシード粒子との複合体、共役系導電性重合体とポリアニオンとの複合体、またはこれら2種の複合体を分散させることができるものであれば特に限定されないが、シード粒子の分散液に用いた水性媒体と同じ種類のものが好ましい。[Aqueous medium]
The aqueous medium used for the polymerization of the monomer compound is a composite of a conjugated conductive polymer and seed particles protected and colloidalized by a polyanion, a composite of a conjugated conductive polymer and a polyanion, or two of these. It is not particularly limited as long as it can disperse the seed complex, but the same kind as the aqueous medium used for the dispersion liquid of the seed particles is preferable.
単量体化合物の重合に用いられる水性媒体としては、水、または水と水溶性溶媒との混合溶媒が挙げられる。
水溶性溶媒としては、例えば、N−ビニルピロリドン、ヘキサメチルホスホルトリアミド、N−ビニルホルムアミド、N−ビニルアセトアミド等のアミド類;クレゾール、フェノール、キシレノール等のフェノール類;メタノール、エタノール、イソプロピルアルコール等の一価アルコール類;エチレングリコール、プロピレングリコール、ジプロピレングリコール、1,3−ブチレングリコール、1,4−ブチレングリコール、ジグリセリン、イソプレングリコール、ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、1,9−ノナンジオール、ネオペンチルグリコール等の多価アルコール類;アセトン等のケトン類;エチレンカーボネート、プロピレンカーボネート等のカーボネート化合物;ジオキサン、ジエチルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールジアルキルエーテル、ポリプロピレングリコールジアルキルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル等のエーテル類;3−メチル−2−オキサゾリジノン等の複素環化合物;アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル類が挙げられる。これらの溶媒は、1種単独でまたは2種以上を組み合わせて用いることができる。Examples of the aqueous medium used for the polymerization of the monomer compound include water or a mixed solvent of water and a water-soluble solvent.
Examples of the water-soluble solvent include amides such as N-vinylpyrrolidone, hexamethylphosphortriamide, N-vinylformamide and N-vinylacetamide; phenols such as cresol, phenol and xylenol; methanol, ethanol, isopropyl alcohol and the like. Monovalent alcohols; ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diglycerin, isoprene glycol, butanediol, 1,5-pentanediol, 1,6- Polyhydric alcohols such as hexanediol, 1,9-nonanediol, neopentyl glycol; ketones such as acetone; carbonate compounds such as ethylene carbonate and propylene carbonate; dioxane, diethyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether , Polypropylene glycol dialkyl ethers, ethylene glycol monomethyl ethers, ethylene glycol monobutyl ethers and other ethers; heterocyclic compounds such as 3-methyl-2-oxazolidinone; acetonitrile, glutalogie nitriles, methoxy acetonitrile, propionitrile, benzonitrile and the like. Examples include nitriles. These solvents can be used alone or in combination of two or more.
水性媒体中での水溶性溶媒の割合は0〜30質量%が好ましい。水性媒体は、水を50質量%以上含むことがより好ましく、水を単独で用いることがさらに好ましい。水溶性溶媒の割合が30質量%以下であると単量体化合物の重合反応を安定化させることができる。 The ratio of the water-soluble solvent in the aqueous medium is preferably 0 to 30% by mass. The aqueous medium more preferably contains 50% by mass or more of water, and further preferably uses water alone. When the proportion of the water-soluble solvent is 30% by mass or less, the polymerization reaction of the monomer compound can be stabilized.
水性媒体の使用量は、単量体化合物、ポリアニオンにより保護コロイド化されたシード粒子、及び保護コロイド化に寄与していないポリアニオンの総計100質量部に対して、好ましくは10〜50,000質量部、より好ましくは50〜10,000質量部である。水性媒体の使用量が10質量部以上であれば重合中の分散液の粘度が適切であり、50,000質量部以下であれば固体電解コンデンサの性能が良好である。 The amount of the aqueous medium used is preferably 10 to 50,000 parts by mass with respect to a total of 100 parts by mass of the monomer compound, the seed particles protected and colloidalized by the polyanion, and the polyanion that does not contribute to the protective colloidalization. , More preferably 50 to 10,000 parts by mass. When the amount of the aqueous medium used is 10 parts by mass or more, the viscosity of the dispersion during polymerization is appropriate, and when it is 50,000 parts by mass or less, the performance of the solid electrolytic capacitor is good.
[酸化剤]
上記単量体化合物の重合において、例えば、ポリピロール類やポリチオフェン類を共役系導電性重合体として含む分散液を製造する場合、酸化剤の存在下に単量体化合物液を所定の温度にすることによって重合が開始される。[Oxidant]
In the polymerization of the above-mentioned monomer compound, for example, in the case of producing a dispersion liquid containing polypyrroles and polythiophenes as a conjugated conductive polymer, the monomer compound liquid is brought to a predetermined temperature in the presence of an oxidizing agent. The polymerization is started by.
酸化剤としては、ペルオキソ二硫酸、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸カリウム等のペルオキソ二硫酸塩;三フッ化ホウ素等の金属ハロゲン化合物;塩化第二鉄、硫酸第二鉄、塩化第二銅等の遷移金属化合物;酸化銀、酸化セシウム等の金属酸化物;過酸化水素、オゾン等の過酸化物;過酸化ベンゾイル等の有機過酸化物;酸素等が挙げられる。これらのうちペルオキソ二硫酸及びペルオキソ二硫酸塩が好ましく、ペルオキソ二硫酸塩がより好ましい。
上記酸化剤は、1種単独でまたは2種以上を組み合わせて用いることができる。Examples of the oxidizing agent include peroxodisulfate such as peroxodisulfuric acid, ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate; metal halogen compounds such as boron trifluoride; ferric chloride, ferric sulfate and chloride. Transition metal compounds such as cupric oxide; metal oxides such as silver oxide and cesium oxide; peroxides such as hydrogen peroxide and ozone; organic peroxides such as benzoyl peroxide; oxygen and the like. Of these, peroxodisulfate and peroxodisulfate are preferable, and peroxodisulfate is more preferable.
The above-mentioned oxidizing agents may be used alone or in combination of two or more.
[重合温度]
上記単量体化合物の重合時の温度は通常、5〜80℃であり、好ましくは10〜60℃であり、より好ましくは15〜40℃である。重合時の温度をこの範囲内にすると、適度な反応速度で重合を行うことができ、反応液の粘度の上昇を抑えることができ、共役系導電性重合体を含む分散液の製造を安定的に経済的な時間で行うことができ、かつ得られる共役系導電性重合体の導電率が高くなる傾向がある。重合時の温度は、公知のヒータやクーラを用いることにより管理することができる。また、必要に応じ、上記範囲内で温度を変化させながら重合を行ってもよい。[Polymerization temperature]
The temperature at the time of polymerization of the above-mentioned monomer compound is usually 5 to 80 ° C, preferably 10 to 60 ° C, and more preferably 15 to 40 ° C. When the temperature at the time of polymerization is within this range, the polymerization can be carried out at an appropriate reaction rate, the increase in the viscosity of the reaction solution can be suppressed, and the production of the dispersion liquid containing the conjugated conductive polymer is stable. It can be carried out in an economical time, and the conductivity of the obtained conjugated conductive polymer tends to be high. The temperature at the time of polymerization can be controlled by using a known heater or cooler. Further, if necessary, the polymerization may be carried out while changing the temperature within the above range.
[保護コロイド化されたシード粒子の分散液の添加]
上記単量体化合物と保護コロイド化されたシード粒子とを含む分散液を用いた上記単量体化合物の重合中に、反応液にポリアニオンにより保護コロイド化されたシード粒子の分散液をさらに添加することが好ましい。上記単量体化合物の重合中に、所定量の保護コロイド化されたシード粒子の分散液をさらに添加することにより、重合時の反応液の増粘を抑制でき撹拌混合効率の向上や製造装置への負荷を低減することができる。重合中に添加する保護コロイド化されたシード粒子の分散液の量は、使用する保護コロイド化されたシード粒子の分散液の総量の10〜90質量%が好ましく、20〜80質量%がより好ましく、30〜70質量%がさらに好ましい。[Addition of dispersion of protective colloidalized seed particles]
During the polymerization of the above-mentioned monomer compound using the dispersion liquid containing the above-mentioned monomer compound and the protective colloidalized seed particles, the dispersion liquid of the protective colloidalized seed particles by a polyanion is further added to the reaction solution. Is preferable. By further adding a predetermined amount of the dispersion liquid of the protective colloidalized seed particles during the polymerization of the above-mentioned monomer compound, the thickening of the reaction liquid at the time of polymerization can be suppressed, the stirring and mixing efficiency can be improved, and the production apparatus Load can be reduced. The amount of the dispersion liquid of the protective colloidalized seed particles added during the polymerization is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total amount of the dispersion liquid of the protective colloidalized seed particles to be used. , 30-70% by mass is more preferable.
[ポリアニオンの添加]
上記単量体化合物の重合中に、反応液にポリアニオンをさらに添加してもよい。上記単量体化合物の重合中に所定量のポリアニオンの一部をさらに添加することにより重合時の反応液の増粘を抑制でき撹拌混合効率の向上や製造装置への負荷を低減することができる。重合中に添加するポリアニオンの量は、使用するポリアニオンの総量の0〜90質量%が好ましく、20〜80質量%がより好ましく、30〜70質量%がさらに好ましい。[Addition of polyanion]
A polyanion may be further added to the reaction solution during the polymerization of the above-mentioned monomer compound. By further adding a part of a predetermined amount of polyanion during the polymerization of the above-mentioned monomer compound, the thickening of the reaction solution at the time of polymerization can be suppressed, the stirring and mixing efficiency can be improved, and the load on the manufacturing apparatus can be reduced. .. The amount of the polyanion added during the polymerization is preferably 0 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, based on the total amount of the polyanion used.
(共役系導電性重合体を含有する分散液(2)の調製)
工程(A)では、上記のように共役系導電性重合体を含む分散液(1)を調製すると共に、前記分散液(1)に分散処理を施すことで、前記共役系導電性重合体を含有する分散液(2)(以下「共役系導電性重合体含有分散液(2)」ともいう。)を得る。(Preparation of dispersion liquid (2) containing conjugated conductive polymer)
In the step (A), the conjugated conductive polymer is obtained by preparing the dispersion (1) containing the conjugated conductive polymer as described above and subjecting the dispersion (1) to a dispersion treatment. A dispersion liquid (2) containing the mixture (hereinafter, also referred to as “conjugated conductive polymer-containing dispersion liquid (2)”) is obtained.
なお、共役系導電性重合体の種類の異なる2種以上の分散液(1)を準備し、これらを混合して得られた分散液に対して分散処理を施してもよい。
前記共役系導電性重合体を含む分散液(1)は、(i)共役系導電性重合体とポリアニオンとの複合体、および(ii)共役系導電性重合体とポリアニオンにより保護コロイド化されたシード粒子との複合体、から選択される少なくとも一つが水性媒体中に分散した分散液である。Two or more kinds of dispersion liquids (1) having different types of conjugated conductive polymers may be prepared, and the dispersion liquid obtained by mixing these may be subjected to a dispersion treatment.
The dispersion liquid (1) containing the conjugated conductive polymer was made into a protective colloid by (i) a composite of the conjugated conductive polymer and the polyanion, and (ii) the conjugated conductive polymer and the polyanion. At least one selected from the composite with the seed particles is a dispersion dispersed in an aqueous medium.
前記重合性化合物の重合の進行とともに前記複合体は凝集することがある。
固体電解コンデンサの静電容量およびESRの向上のためには(つまり、固体電解コンデンサの静電容量を大きくし、ESRを低減させるためには)、多孔性陽極体への含浸性を向上させる必要があるため、本発明においては、工程(A)において複合体を解砕し、平均粒子径が1〜10μmの微粒子が分散された状態とする。The complex may aggregate as the polymerization of the polymerizable compound progresses.
In order to improve the capacitance and ESR of the solid electrolytic capacitor (that is, to increase the capacitance of the solid electrolytic capacitor and reduce the ESR), it is necessary to improve the impregnation property into the porous anode. Therefore, in the present invention, the composite is crushed in the step (A) so that fine particles having an average particle size of 1 to 10 μm are dispersed.
[分散処理]
分散処理は、前記複合体を前記微粒子の大きさまで解砕するものであり、ホモジナイザー等の強力な撹拌装置や超音波照射によって行うことが好ましい。分散処理は前記重合性化合物を重合する際に行ってもよい。すなわち、分散処理が施される分散液(1)には、未反応の前記重合性化合物が含まれていてもよい。例えば、特開2007−332183号公報にはせん断速度5,000s-1以上で撹拌しながら共役系導電性重合体を重合させる方法が記載されている。[Distributed processing]
The dispersion treatment is for crushing the complex to the size of the fine particles, and is preferably performed by a powerful stirring device such as a homogenizer or ultrasonic irradiation. The dispersion treatment may be carried out when polymerizing the polymerizable compound. That is, the dispersion liquid (1) to be subjected to the dispersion treatment may contain the unreacted polymerizable compound. For example, Japanese Patent Application Laid-Open No. 2007-332183 describes a method of polymerizing a conjugated conductive polymer while stirring at a shear rate of 5,000 s- 1 or higher.
超音波照射の場合、分散処理液あたりの消費電力5〜500W/Lで行うことが好ましい。分散処理は、フロー方式でもバッチ方式でもどちらでもよい。
高圧ホモジナイザーを使用する場合、高圧ホモジナイザーの圧力は、好ましくは10〜2000barであり、より好ましくは20〜1500barであり、さらに好ましくは50〜1000barである。高圧ホモジナイザーの圧力が10bar以上であれば、分散処理が効率的に行われ、固体電解コンデンサの性能が良好である。高圧ホモジナイザーの圧力が2000bar以下であれば、分散処理の際の作業性が良好である。In the case of ultrasonic irradiation, it is preferable to perform the power consumption per dispersion treatment liquid at 5 to 500 W / L. The distributed processing may be either a flow method or a batch method.
When a high pressure homogenizer is used, the pressure of the high pressure homogenizer is preferably 10 to 2000 bar, more preferably 20 to 1500 bar, still more preferably 50 to 1000 bar. When the pressure of the high-voltage homogenizer is 10 bar or more, the dispersion treatment is efficiently performed and the performance of the solid electrolytic capacitor is good. When the pressure of the high-pressure homogenizer is 2000 bar or less, the workability during the dispersion treatment is good.
例えば、分散処理能力が500ml/分の高圧ホモジナイザーを用いて、1500mlの分散液を分散処理する場合、分散液全量を1回分散処理するのに必要な時間は3分となる。分散処理時間は、好ましくは合計15〜900分であり、より好ましくは30〜600分であり、さらに好ましくは60〜300分である。高圧ホモジナイザーの分散処理時間が15分以上であれば、分散処理の効果が発現され、固体電解コンデンサの性能が良好である。高圧ホモジナイザーの分散処理時間が900分以下であれば、分散処理の効率性が良好である。 For example, when a 1500 ml dispersion is dispersed using a high-pressure homogenizer having a dispersion processing capacity of 500 ml / min, the time required to disperse the entire amount of the dispersion once is 3 minutes. The dispersion treatment time is preferably a total of 15 to 900 minutes, more preferably 30 to 600 minutes, and even more preferably 60 to 300 minutes. When the dispersion treatment time of the high-voltage homogenizer is 15 minutes or more, the effect of the dispersion treatment is exhibited and the performance of the solid electrolytic capacitor is good. When the dispersion treatment time of the high-pressure homogenizer is 900 minutes or less, the efficiency of the dispersion treatment is good.
分散処理を一時停止する時間は、合計1〜6000分であり、より好ましくは6〜2250分であり、さらに好ましくは20〜750分である。分散処理を一時停止する時間が合計2分以上であれば、固体電解コンデンサの性能が良好である。分散処理を一時停止する時間が6000分以下であれば、作業性が良好である。 The total time for suspending the dispersion processing is 1 to 6000 minutes, more preferably 6 to 2250 minutes, and further preferably 20 to 750 minutes. If the total time for suspending the dispersion processing is 2 minutes or more, the performance of the solid electrolytic capacitor is good. If the time to suspend the distributed processing is 6000 minutes or less, the workability is good.
[分散液の濃度]
分散処理を行うときの分散液(1)中の共役系導電性重合体の濃度は、分散処理における生産性を損なわない範囲で、とくに限定はされないが、固体電解コンデンサへの含浸性の観点から、仕上がりの濃度、すなわち工程(A)により得られる分散液(2)中の共役系導電性重合体の濃度は1.0〜10.0質量%が好ましい。1.0質量%以上であれば、固体電解コンデンサのESRが良好である(つまり、ESRをより低くすることができる。)。10.0質量%以下であれば、静電容量が良好である(つまり、静電容量をより大きくすることができる。)。[Concentration of dispersion]
The concentration of the conjugated conductive polymer in the dispersion liquid (1) when the dispersion treatment is performed is not particularly limited as long as the productivity in the dispersion treatment is not impaired, but from the viewpoint of impregnation property into the solid electrolytic capacitor. The concentration of the finished product, that is, the concentration of the conjugated conductive polymer in the dispersion liquid (2) obtained in the step (A) is preferably 1.0 to 10.0% by mass. When it is 1.0% by mass or more, the ESR of the solid electrolytic capacitor is good (that is, the ESR can be made lower). When it is 10.0% by mass or less, the capacitance is good (that is, the capacitance can be made larger).
水性媒体で希釈することで分散液(1)中の共役系導電性重合体の濃度を下げてもよい。希釈のタイミングは、分散処理の前、分散処理の途中、分散処理の後のいずれでも構わないが、分散処理の途中に行うことが好ましい。分散処理の途中で水性媒体により希釈することで、高濃度で効率よく分散処理を行うことができ、希釈による再凝集の影響を軽減できる。 The concentration of the conjugated conductive polymer in the dispersion liquid (1) may be lowered by diluting with an aqueous medium. The timing of dilution may be before the dispersion treatment, during the dispersion treatment, or after the dispersion treatment, but it is preferably performed during the dispersion treatment. By diluting with an aqueous medium during the dispersion treatment, the dispersion treatment can be efficiently performed at a high concentration, and the influence of reaggregation due to the dilution can be reduced.
<分散処理の一時停止>
工程(A)においては、前記分散処理を一時停止する操作が1回以上、合計1〜6000分行われる。<Pause of distributed processing>
In the step (A), the operation of suspending the dispersion processing is performed once or more, for a total of 1 to 6000 minutes.
[分散処理の一時停止]
一時的に前記分散処理を停止し、分散液(1)を静置することで、分散していた複合体および/またはその解砕物(以下「複合体等」とも記載する。)は凝集し、分散液(1)は増粘する。増粘後に再度分散処理を行うことで、複合体等の解凝集を促進させることができる。[Pause distributed processing]
By temporarily stopping the dispersion treatment and allowing the dispersion liquid (1) to stand, the dispersed complex and / or its crushed material (hereinafter, also referred to as “complex or the like”) is aggregated and aggregated. The dispersion liquid (1) thickens. By performing the dispersion treatment again after thickening, deagglomeration of the complex and the like can be promoted.
複合体等の解凝集の促進により固体電解コンデンサの静電容量及びESRが向上する原因(つまり、静電容量が大きくなりESRが低減する理由)の詳細は不明であるが、複合体等の表面における共役系導電性重合体の存在率に変化が生じると推測される。 The details of the reason why the capacitance and ESR of the solid electrolytic capacitor are improved by promoting the deagglomeration of the composite or the like (that is, the reason why the capacitance is increased and the ESR is reduced) are unknown, but the surface of the composite or the like is unknown. It is presumed that the abundance of the conjugated conductive polymer in the above will change.
分散処理を一時停止する操作は、1回行ってもよく、複数回行ってもよい。好ましくは2〜20回、より好ましくは3〜15回、さらに好ましくは4〜10回である。
1回あたりの一時停止の時間としては、1〜300分が好ましく、2〜150分がより好ましく、5〜75分がさらに好ましい。分散処理を一時停止する時間が1分以上であれば、分散処理が効率的に行われ、良好な性能の固体電解コンデンサが製造される。The operation of suspending the distributed processing may be performed once or a plurality of times. It is preferably 2 to 20 times, more preferably 3 to 15 times, still more preferably 4 to 10 times.
The pause time per pause is preferably 1 to 300 minutes, more preferably 2 to 150 minutes, and even more preferably 5 to 75 minutes. If the time for suspending the dispersion processing is 1 minute or more, the dispersion processing is efficiently performed, and a solid electrolytic capacitor having good performance is manufactured.
分散処理を一時的に停止する時間が300分以下であれば、分散処理の際の作業性が良好である。
増粘させた分散液の粘度(たとえば、一時停止終了時の粘度)は、好ましくは、増粘させる前の粘度(たとえば、一時停止開始時の粘度)の1.05〜100.0倍の粘度であり、さらに好ましくは1.10〜50.0倍の粘度であり、より好ましくは1.50〜50.0倍の粘度であり、特に好ましくは3.00〜50.0倍の粘度であり、上限はたとえば15倍であってもよい。増粘後の分散液の粘度が増粘させる前の粘度の1.05倍以上であれば、共役系導電性重合体の解凝集が効率的に行われ、固体電解コンデンサの性能が良好である。増粘後の分散液の粘度が増粘させる前の粘度の100.0倍以下であれば、分散処理の効率性が良好である。If the time for temporarily stopping the distributed processing is 300 minutes or less, the workability during the distributed processing is good.
The viscosity of the thickened dispersion (for example, the viscosity at the end of the pause) is preferably 1.05 to 100.0 times the viscosity before the thickening (for example, the viscosity at the start of the pause). It is more preferably 1.10 to 50.0 times the viscosity, more preferably 1.50 to 50.0 times the viscosity, and particularly preferably 3.00 to 50.0 times the viscosity. The upper limit may be, for example, 15 times. If the viscosity of the dispersion after thickening is 1.05 times or more the viscosity before thickening, the conjugated conductive polymer is efficiently deagglomerated and the performance of the solid electrolytic capacitor is good. .. When the viscosity of the dispersion liquid after thickening is 100.0 times or less the viscosity before thickening, the efficiency of the dispersion treatment is good.
[塩化合物の添加]
工程(A)において、水性媒体に塩化合物を添加することもできる。塩化合物の添加により分散液のイオン強度を高め、分散していた複合体を凝集させ、分散液(1)をさらに増粘させることが可能となる。[Addition of salt compounds]
In step (A), the salt compound can also be added to the aqueous medium. By adding the salt compound, the ionic strength of the dispersion liquid can be increased, the dispersed complex can be aggregated, and the dispersion liquid (1) can be further thickened.
塩化合物を添加するタイミングは特に制限は無いが、均一性を確保するため、単量体化合物の重合における撹拌中、又は分散液(1)の分散処理中が好ましい。なお、後述の脱塩を行う場合、脱塩後に再び塩化合物を添加して分散してもよい。分散液(1)の分散処理中に塩化合物を添加することが好ましく、分散処理終了の10分前までに添加することがより好ましい。
The timing of adding the salt compound is not particularly limited, but in order to ensure uniformity, it is preferable during stirring in the polymerization of the monomer compound or during the dispersion treatment of the dispersion liquid (1). When desalting, which will be described later, may be carried out, a salt compound may be added again and dispersed after desalting. It is preferable to add the salt compound during the dispersion treatment of the dispersion liquid (1), and it is more preferable to add the
塩化合物としては、水性媒体に溶解し、分散液のイオン強度を高め、分散液を増粘させるものであれば特に制限されない。
例えば、水性媒体に溶解し、分散液のイオン強度を高め、分散液を増粘させる無機塩及び有機塩から選ばれる少なくとも一種の塩化合物であることが好ましい。The salt compound is not particularly limited as long as it dissolves in an aqueous medium, increases the ionic strength of the dispersion, and thickens the dispersion.
For example, it is preferably at least one salt compound selected from inorganic salts and organic salts that dissolve in an aqueous medium, increase the ionic strength of the dispersion, and thicken the dispersion.
有機塩としては、クエン酸塩、乳酸塩、グリコール酸塩、グルコン酸塩、酢酸塩、プロピオン酸塩、フマル酸塩、シュウ酸塩および酒石塩などが挙げられ、より具体的には酢酸カルシウム、酢酸マグネシウムなどが挙げられるが、これらに限定されない。 Examples of the organic salt include citrate, lactate, glycolate, gluconate, acetate, propionate, fumarate, oxalate and tartrate salt, and more specifically, calcium acetate. , Magnesium acetate and the like, but are not limited thereto.
無機塩としては、塩酸塩、炭酸塩、炭酸水素塩、硫酸塩、リン酸水素塩、およびリン酸塩などが挙げられ、より具体的には塩化アルミニウム、硝酸ナトリウム、硫酸マグネシウム、硫酸アルミニウム、硫酸アンモニウム、硫酸カリウム、硫酸ナトリウム等が挙げられるが、これらに限定されない。これらの塩化合物は、1種を単独で用いてもよく、2種以上を併用してもよい。 Examples of the inorganic salt include hydrochloride, carbonate, bicarbonate, sulfate, hydrogen phosphate, phosphate and the like, and more specifically, aluminum chloride, sodium nitrate, magnesium sulfate, aluminum sulfate, ammonium sulfate and the like. , Potassium sulfate, sodium sulfate and the like, but are not limited thereto. One of these salt compounds may be used alone, or two or more thereof may be used in combination.
添加量は分散液(2)の総量(100質量%)に対して0.01〜30質量%となる量が好ましく、0.01〜15質量%となる量がさらに好ましく、0.01〜5質量%となる量がより好ましい。添加量が0.01質量%以上であれば、分散液(1)の増粘が十分であり、30質量%以下であれば、分散処理の効率性が良好である。 The addition amount is preferably 0.01 to 30% by mass, more preferably 0.01 to 15% by mass, and 0.01 to 5% with respect to the total amount (100% by mass) of the dispersion liquid (2). The amount to be mass% is more preferable. When the addition amount is 0.01% by mass or more, the thickening of the dispersion liquid (1) is sufficient, and when it is 30% by mass or less, the efficiency of the dispersion treatment is good.
[添加剤]
共役系導電性重合体を含む分散液(1)には、必要に応じて種々の添加剤を添加することができる。添加剤は、共役系導電性重合体、及びポリアニオンにより保護コロイド化されたシード粒子若しくはポリアニオンと混合しうるものであれば特に制限されない。[Additive]
Various additives can be added to the dispersion liquid (1) containing the conjugated conductive polymer, if necessary. The additive is not particularly limited as long as it can be mixed with the conjugated conductive polymer and the seed particles or the polyanion protected and colloidalized by the polyanion.
このような添加剤としては、例えば、中和剤、水溶性高分子化合物、水分散性化合物、アルカリ性化合物、界面活性剤、消泡剤、カップリング剤、酸化防止剤、電気伝導率向上剤が挙げられる。これらの添加剤は、1種単独でまたは2種以上を組み合わせて用いることができる。 Examples of such additives include neutralizing agents, water-soluble polymer compounds, water-dispersible compounds, alkaline compounds, surfactants, defoaming agents, coupling agents, antioxidants, and electrical conductivity improvers. Can be mentioned. These additives can be used alone or in combination of two or more.
水溶性高分子化合物は、高分子の主鎖または側鎖にカチオン性基やノニオン性基を有する水溶性ポリマーである。水溶性高分子化合物の具体例としては、ポリオキシアルキレン、水溶性ポリウレタン、水溶性ポリエステル、水溶性ポリアミド、水溶性ポリイミド、水溶性ポリアクリル、水溶性ポリアクリルアミド、ポリビニルアルコール、ポリアクリル酸が挙げられる。これらのうち、ポリオキシアルキレンが好ましい。 A water-soluble polymer compound is a water-soluble polymer having a cationic group or a nonionic group in the main chain or side chain of the polymer. Specific examples of the water-soluble polymer compound include polyoxyalkylene, water-soluble polyurethane, water-soluble polyester, water-soluble polyamide, water-soluble polyimide, water-soluble polyacrylic, water-soluble polyacrylamide, polyvinyl alcohol, and polyacrylic acid. .. Of these, polyoxyalkylene is preferable.
ポリオキシアルキレンの具体例としては、ジエチレングリコール、トリエチレングリコール、オリゴポリエチレングリコール、トリエチレングリコールモノクロルヒドリン、ジエチレングリコールモノクロルヒドリン、オリゴエチレングリコールモノクロルヒドリン、トリエチレングリコールモノブロムヒドリン、ジエチレングリコールモノブロムヒドリン、オリゴエチレングリコールモノブロムヒドリン、ポリエチレングリコール、グリシジルエーテル類、ポリエチレングリコールグリシジルエーテル類、ポリエチレンオキシド、トリエチレングリコール・ジメチルエーテル、テトラエチレングリコール・ジメチルエーテル、ジエチレングリコール・ジメチルエーテル、ジエチレングリコール・ジエチルエーテル・ジエチレングリコール・ジブチルエーテル、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール、ポリプロピレンジオキシド、ポリオキシエチレンアルキルエーテル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸アミドが挙げられる。 Specific examples of the polyoxyalkylene include diethylene glycol, triethylene glycol, oligopolyethylene glycol, triethylene glycol monochlorohydrin, diethylene glycol monochlorohydrin, oligoethylene glycol monochlorohydrin, triethylene glycol monobromhydrin, diethylene glycol monobromhydrin, and the like. Oligoethylene glycol monobromhydrin, polyethylene glycol, glycidyl ethers, polyethylene glycol glycidyl ethers, polyethylene oxide, triethylene glycol / dimethyl ether, tetraethylene glycol / dimethyl ether, diethylene glycol / dimethyl ether, diethylene glycol / diethyl ether / diethylene glycol / dibutyl ether, di Examples thereof include propylene glycol, tripropylene glycol, polypropylene glycol, polypropylene dioxide, polyoxyethylene alkyl ether, polyoxyethylene glycerin fatty acid ester, and polyoxyethylene fatty acid amide.
水分散性化合物は、親水性の低い化合物の一部が親水性の高い官能基で置換されたもの、あるいは、親水性の低い化合物の周囲に親水性の高い官能基を有する化合物が吸着したもの(例えばエマルジョン等)であって、水中で沈殿せずに分散するものが挙げられる。具体例としては、ポリエステル、ポリウレタン、アクリル樹脂、シリコーン樹脂、及びこれらポリマーのエマルジョンが挙げられる。また、アクリル樹脂とポリエステルやポリウレタン等の他の共重合体とのブロック共重合体やグラフト共重合体が挙げられる。 The water-dispersible compound is a compound in which a part of a compound having a low hydrophilicity is replaced with a functional group having a high hydrophilicity, or a compound in which a compound having a high hydrophilicity group is adsorbed around a compound having a low hydrophilicity. Examples thereof include those (for example, emulsions) that are dispersed in water without being precipitated. Specific examples include polyester, polyurethane, acrylic resin, silicone resin, and emulsions of these polymers. Further, block copolymers and graft copolymers of acrylic resin and other copolymers such as polyester and polyurethane can be mentioned.
水溶性高分子化合物及び水分散性化合物は、1種単独でまたは2種以上を組み合わせて用いることができる。水溶性高分子化合物及び水分散性化合物を添加することにより、導電性重合体を含む分散液の粘度調節ができ、また塗布性能を向上させることができる。 The water-soluble polymer compound and the water-dispersible compound may be used alone or in combination of two or more. By adding the water-soluble polymer compound and the water-dispersible compound, the viscosity of the dispersion liquid containing the conductive polymer can be adjusted, and the coating performance can be improved.
水溶性高分子化合物及び水分散性化合物の使用量は、共役系導電性重合体とポリアニオンにより保護コロイド化されたシード粒子との合計100質量部に対して、好ましくは10〜100,000質量部、より好ましくは25〜50,000質量部、さらに好ましくは50〜20,000質量部である。水溶性高分子化合物及び水分散性化合物の量が10〜100,000質量部の範囲にあると適正な導電性を発現させることができ、良好な固体電解コンデンサの等価直列抵抗(ESR)が得られる(つまり、ESRを低減できる。)。 The amount of the water-soluble polymer compound and the water-dispersible compound used is preferably 100 to 100,000 parts by mass with respect to 100 parts by mass in total of the conjugated conductive polymer and the seed particles protected and colloidalized by the polyanion. , More preferably 25 to 50,000 parts by mass, still more preferably 50 to 20,000 parts by mass. When the amount of the water-soluble polymer compound and the water-dispersible compound is in the range of 10 to 100,000 parts by mass, appropriate conductivity can be exhibited and the equivalent series resistance (ESR) of a good solid electrolytic capacitor can be obtained. (That is, ESR can be reduced).
アルカリ性化合物として、公知の無機アルカリ性化合物や有機アルカリ性化合物を使用できる。無機アルカリ性化合物としては、例えば、アンモニア、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、アンモニアが挙げられる。有機アルカリ性化合物として、芳香族アミン、脂肪族アミン、アルカリ金属アルコキシド等が挙げられる。アルカリ性化合物の添加によって分散液を適用した物品に耐腐食性を付与することでき、また共役系導電性重合体含有分散液のpHを調整することができる。 As the alkaline compound, a known inorganic alkaline compound or organic alkaline compound can be used. Examples of the inorganic alkaline compound include ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia. Examples of the organic alkaline compound include aromatic amines, aliphatic amines, and alkali metal alkoxides. Corrosion resistance can be imparted to the article to which the dispersion has been applied by adding an alkaline compound, and the pH of the conjugated conductive polymer-containing dispersion can be adjusted.
芳香族アミンの中では、窒素含有ヘテロアリール環化合物が好ましい。窒素含有ヘテロアリール環化合物は芳香族性を示す窒素含有ヘテロ環化合物である。芳香族アミンにおいては、ヘテロ環に含まれる窒素原子が他の原子と共役関係を持つ。 Among aromatic amines, nitrogen-containing heteroaryl ring compounds are preferred. The nitrogen-containing heteroaryl ring compound is a nitrogen-containing heterocyclic compound exhibiting aromaticity. In aromatic amines, the nitrogen atom contained in the heterocycle has a conjugated relationship with other atoms.
窒素含有ヘテロアリール環化合物としては、例えば、ピリジン類、イミダゾール類、ピリミジン類、ピラジン類、トリアジン類が挙げられる。これらの中でも、溶媒溶解性等の観点から、ピリジン類、イミダゾール類、ピリミジン類が好ましい。 Examples of the nitrogen-containing heteroaryl ring compound include pyridines, imidazoles, pyrimidines, pyrazines, and triazines. Among these, pyridines, imidazoles, and pyrimidines are preferable from the viewpoint of solvent solubility and the like.
脂肪族アミンとしては、例えば、エチルモルホリン、エチルアミン、n−オクチルアミン、ジエチルアミン、ジイソブチルアミン、メチルエチルアミン、トリメチルアミン、トリエチルアミン、アリルアミン、2−エチルアミノエタノール、2,2'−イミノジエタノール、N−エチルエチレンジアミンが挙げられる。 Examples of the aliphatic amine include ethylmorpholine, ethylamine, n-octylamine, diethylamine, diisobutylamine, methylethylamine, trimethylamine, triethylamine, allylamine, 2-ethylaminoethanol, 2,2'-iminodiethanol, and N-ethylethylenediamine. Can be mentioned.
アルカリ金属アルコキシドとしては、例えば、ナトリウムメトキシド、ナトリウムエトキシド等のナトリウムアルコキシド、カリウムアルコキシド、カルシウムアルコキシドが挙げられる。 Examples of the alkali metal alkoxide include sodium alkoxides such as sodium methoxide and sodium ethoxide, potassium alkoxides, and calcium alkoxides.
界面活性剤としては、例えば、カルボン酸塩、スルホン酸塩、硫酸エステル塩、燐酸エステル塩等の陰イオン界面活性剤;アミン塩、4級アンモニウム塩等の陽イオン界面活性剤;カルボキシベタイン、アミノカルボン酸塩、イミダゾリウムベタイン等の両性界面活性剤;ポリオキシエチレンアルキルエーテル、ポリオキシエチレングリセリン脂肪酸エステル、エチレングリコール脂肪酸エステル、ポリオキシエチレン脂肪酸アミド等の非イオン界面活性剤が挙げられる。 Examples of the surfactant include anionic surfactants such as carboxylate, sulfonate, sulfate ester salt and phosphoric acid ester salt; cationic surfactants such as amine salt and quaternary ammonium salt; carboxybetaine and amino. Amphoteric surfactants such as carboxylates and imidazolium betaine; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, ethylene glycol fatty acid esters and polyoxyethylene fatty acid amides.
消泡剤としては、例えば、シリコーン樹脂、ポリジメチルシロキサン、シリコーンレジンが挙げられる。
酸化防止剤としては、例えば、フェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、糖類、ビタミン類が挙げられる。Examples of the defoaming agent include silicone resin, polydimethylsiloxane, and silicone resin.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, sugars, and vitamins.
電気伝導率向上剤は、導電性重合体を含む分散液の電気伝導率を増大させるものであれば特に制限されない。電気伝導率向上剤としては、例えば、テトラヒドロフラン等のエーテル結合を含む化合物;γ−ブチロラクトン、γ−バレロラクトン等のラクトン基を含む化合物;カプロラクタム、N−メチルカプロラクタム、N,N−ジメチルアセトアミド、N−メチルアセトアミド、N,N−ジメチルホルムアミド、N−メチルホルムアミド、N−メチルホルムアニリド、N−メチルピロリドン、N−オクチルピロリドン、ピロリドン等のアミド若しくはラクタム基を含む化合物;テトラメチレンスルホン、ジメチルスルホキシド等のスルホン化合物若しくはスルホキシド化合物;スクロース、グルコース、フルクトース、ラクトース等の糖類または糖類誘導体;ソルビトール、マンニトール等の糖アルコール類;スクシンイミド、マレイミド等のイミド類;2−フランカルボン酸、3−フランカルボン酸等のフラン誘導体;エチレングリコール、プロピレングリコール、グリセリン、ジエチレングリコール、トリエチレングリコール等のジアルコール若しくはポリアルコールが挙げられる。これらの中でも、電気伝導率向上の観点から、テトラヒドロフラン、N−メチルホルムアミド、N−メチルピロリドン、エチレングリコール、プロピレングリコール、グリセリン、ジメチルスルホキシド、ソルビトールが好ましく、中でもエチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、及びグリセリンがより好ましい。電気伝導率向上剤は、1種単独でまたは2種以上を組み合わせて用いることができる。 The electric conductivity improving agent is not particularly limited as long as it increases the electric conductivity of the dispersion liquid containing the conductive polymer. Examples of the electric conductivity improver include compounds containing an ether bond such as tetrahydrofuran; compounds containing a lactone group such as γ-butyrolactone and γ-valerolactone; caprolactam, N-methylcaprolactam, N, N-dimethylacetamide, and N. -Methylacetamide, N, N-dimethylformamide, N-methylformamide, N-methylformanilide, N-methylpyrrolidone, N-octylpyrrolidone, pyrrolidone and other compounds containing amides or lactam groups; tetramethylenesulfone, dimethylsulfoxide, etc. Sulfone compounds or sulfoxide compounds; saccharides or saccharide derivatives such as sucrose, glucose, fructose, lactos; sugar alcohols such as sorbitol, mannitol; imides such as succinimide, maleimide; 2-furancarboxylic acid, 3-furancarboxylic acid, etc. Fran derivatives; examples thereof include dialcohols or polyalcohols such as ethylene glycol, propylene glycol, glycerin, diethylene glycol and triethylene glycol. Among these, tetrahydrofuran, N-methylformamide, N-methylpyrrolidone, ethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, and sorbitol are preferable from the viewpoint of improving electrical conductivity, and among them, ethylene glycol, diethylene glycol, triethylene glycol, and propylene are preferable. Glycol and glycerin are more preferred. The electric conductivity improver may be used alone or in combination of two or more.
[脱塩]
分散液(1)が塩を含む場合には、前記分散処理を終えた後に分散液(1)を脱塩してもよい。工程(A)で一次粒子まで分散された共役系導電性重合体及びポリアニオンの複合体は、脱塩することにより静置しても分散性を保つことができる。
脱塩の方法に特に制限は無く、透析法、遠心分離洗浄法、イオン交換法等により脱塩を行うことができる。[Desalting]
When the dispersion liquid (1) contains a salt, the dispersion liquid (1) may be desalted after the dispersion treatment is completed. The composite of the conjugated conductive polymer and the polyanion dispersed up to the primary particles in the step (A) can maintain the dispersibility even if it is allowed to stand by desalting.
The desalting method is not particularly limited, and desalting can be performed by a dialysis method, a centrifugal washing method, an ion exchange method, or the like.
<多孔性陽極体に共役系導電性重合体含有分散液(2)を付着させる工程(B)>
本発明の固体電解コンデンサの製造方法は、前述の工程(A)で得られた共役系導電性重合体含有分散液(2)を、弁金属からなる陽極体と、該陽極体表面の少なくとも一部に形成された誘電体被膜とを有する多孔性陽極体の表面に付着させる工程(B)を有する。<Step (B) of Adhering Conjugated Conductive Polymer-Containing Dispersion Liquid (2) to Porous Anode
In the method for producing a solid electrolytic capacitor of the present invention, the conjugated conductive polymer-containing dispersion liquid (2) obtained in the above-mentioned step (A) is subjected to an anode made of a valve metal and at least one of the surface of the anode. It has a step (B) of adhering to the surface of a porous anode having a dielectric film formed on the portion.
本発明の製造方法に係る固体電解コンデンサは、例えば、高表面積を有する弁金属粉末を焼結してなる多孔性の電極、あるいは弁金属箔をエッチングし得られる多孔性膜を電極とすることができる。 The solid electrolytic capacitor according to the manufacturing method of the present invention may have, for example, a porous electrode made by sintering a valve metal powder having a high surface area, or a porous film obtained by etching a valve metal foil as an electrode. it can.
上記弁金属としては、アルミニウム(Al)、ベリリウム(Be)、ビスマス(Bi)、マグネシウム(Mg)、ゲルマニウム(Ge)、ハフニウム(Hf)、ニオブ(Nb)、アンチモン(Sb)、ケイ素(Si)、スズ(Sn)、タンタル(Ta)、チタン(Ti)、バナジウム(V)、タングステン(W)及びジルコニウム(Zr)、ならびにこれらの金属の少なくとも1つと他の元素との合金または化合物が挙げられる。中でもAl、Nb、またはTaの弁金属から構成される電極材料が好ましい。
弁金属からなる多孔性電極は、例えば、陽極酸化によって表面に誘電体酸化被膜を形成し、多孔性陽極体とする。Examples of the valve metal include aluminum (Al), beryllium (Be), bismuth (Bi), magnesium (Mg), germanium (Ge), hafnium (Hf), niobium (Nb), antimony (Sb), and silicon (Si). , Tin (Sn), tantalum (Ta), titanium (Ti), vanadium (V), tungsten (W) and zirconium (Zr), and alloys or compounds of at least one of these metals with other elements. .. Of these, an electrode material composed of a valve metal of Al, Nb, or Ta is preferable.
A porous electrode made of a valve metal, for example, forms a dielectric oxide film on the surface by anodizing to form a porous anode.
上記多孔性電極は、例えばリン酸溶液中で電圧を印加することにより陽極酸化され、多孔性電極の表面に誘電体酸化被膜を形成することができる。誘電体酸化被膜の厚さやコンデンサの耐電圧により、化成電圧の大きさを決めることができる。好ましい化成電圧は1〜800Vであり、より好ましくは1〜300Vである。 The porous electrode is anodized by applying a voltage in a phosphoric acid solution, for example, and a dielectric oxide film can be formed on the surface of the porous electrode. The magnitude of the chemical conversion voltage can be determined by the thickness of the dielectric oxide film and the withstand voltage of the capacitor. The preferred chemical conversion voltage is 1 to 800 V, more preferably 1 to 300 V.
次いで、共役系導電性重合体含有分散液(2)を多孔性陽極体に付着させる。付着させる方法としては、塗布、噴霧、浸漬等の公知の方法が挙げられる。中でも共役系導電性重合体含有分散液(2)を多孔性陽極体にムラなく均一に付着、浸透させることができる点から、浸漬させる方法が好ましい。また、共役系導電性重合体含有分散液(2)を多孔性陽極体の細部まで含侵させるために、減圧下で含侵してもよい。
浸漬時間は、通常10秒〜5分間であり、共役系導電性重合体含有分散液(2)の温度は、水性媒体の種類にもよるが通常10〜35℃である。Next, the conjugated conductive polymer-containing dispersion (2) is attached to the porous anode. Examples of the method of adhering include known methods such as coating, spraying, and dipping. Above all, the immersion method is preferable because the conjugated conductive polymer-containing dispersion liquid (2) can be evenly and uniformly adhered to and permeated into the porous anode body. Further, the conjugated conductive polymer-containing dispersion liquid (2) may be impregnated under reduced pressure in order to impregnate the details of the porous anode.
The immersion time is usually 10 seconds to 5 minutes, and the temperature of the conjugated conductive polymer-containing dispersion (2) is usually 10 to 35 ° C., although it depends on the type of the aqueous medium.
<固体電解質層を形成する工程(C)>
本発明の固体電解コンデンサの製造方法は、前述の工程(B)で得られた多孔性陽極体に付着した共役系導電性重合体含有分散液(2)から、水性媒体を除去し固体電解質層を形成する工程(C)を有する。本工程(C)における水性媒体の除去は、水性媒体の全てを除去することを意味するものでなく、固体電解コンデンサの製造に影響しない範囲で水性媒体が一部残存してもいて差し支えない。<Step of forming a solid electrolyte layer (C)>
In the method for producing a solid electrolytic capacitor of the present invention, the aqueous medium is removed from the conjugated conductive polymer-containing dispersion liquid (2) attached to the porous anode obtained in the above step (B), and the solid electrolyte layer is used. It has a step (C) of forming. The removal of the aqueous medium in this step (C) does not mean that all of the aqueous medium is removed, and a part of the aqueous medium may remain as long as it does not affect the production of the solid electrolytic capacitor.
水性媒体の除去方法としては、効率性の点から加熱処理による乾燥が好ましい。加熱条件は、水性媒体の沸点や揮発性を考慮して決めることができる。加熱は、導電性重合体の酸素による劣化のない温度範囲、例えば、10〜300℃、好ましくは50〜200℃で行うことが好ましい。加熱処理時間は5秒〜数時間が好ましい。加熱処理は、例えば、ホットプレート、オーブン、熱風乾燥機を用いて大気下で、もしくは加熱処理を迅速に行うために減圧下で行ってもよい。 As a method for removing the aqueous medium, drying by heat treatment is preferable from the viewpoint of efficiency. The heating conditions can be determined in consideration of the boiling point and volatility of the aqueous medium. The heating is preferably carried out in a temperature range in which the conductive polymer is not deteriorated by oxygen, for example, 10 to 300 ° C., preferably 50 to 200 ° C. The heat treatment time is preferably 5 seconds to several hours. The heat treatment may be performed, for example, in the atmosphere using a hot plate, an oven, or a hot air dryer, or under reduced pressure for rapid heat treatment.
本発明では、電極体の種類に応じて、上述の共役系導電性重合体含有分散液(2)を付着させる工程(B)と固体電解質層を形成する工程(C)を1回または2回以上繰り返し行ってもよい。ただし、2回目以降の工程(B)では、工程(C)で形成された固体電解質層の表面に分散液(2)を付着させる。分散液を付着させるごとに加熱処理を行い、水性媒体の一部または全部を除去してもよく、または複数回分散液を連続で付着させ、最後に水性媒体を除去してもよい。さらに、付着させた分散液に含まれる水性媒体の一部はまたは全部を除去した後に、任意の電解液を含浸させてもよい。 In the present invention, the step (B) for adhering the above-mentioned conjugated conductive polymer-containing dispersion (2) and the step (C) for forming the solid electrolyte layer are performed once or twice depending on the type of the electrode body. The above may be repeated. However, in the second and subsequent steps (B), the dispersion liquid (2) is adhered to the surface of the solid electrolyte layer formed in the step (C). The heat treatment may be performed each time the dispersion liquid is adhered to remove a part or all of the aqueous medium, or the dispersion liquid may be continuously adhered a plurality of times and finally the aqueous medium may be removed. Further, any electrolytic solution may be impregnated after removing a part or all of the aqueous medium contained in the adhered dispersion.
以上の工程(A)〜(C)を経ることにより、表面に誘電体被膜を有する弁作用金属からなる多孔性陽極体と、前記誘電体被膜の表面に設けられた固体電解質層とを有する固体電解コンデンサが製造される。 Through the above steps (A) to (C), a solid having a porous anode made of a valve acting metal having a dielectric film on its surface and a solid electrolyte layer provided on the surface of the dielectric film. Electrolytic capacitors are manufactured.
以下に実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの例により限定されるものではない。実施例及び比較例における分散液の各物性の測定方法は下記の通りである。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. The methods for measuring the physical properties of the dispersions in Examples and Comparative Examples are as follows.
(1)固形分濃度
各例の固形分濃度は、各例で得られた試料10gを、赤外線水分計((株)ケツト科学研究所製、形式FD−720、加熱条件110℃/30分)を用いて測定し、蒸発残分を固形分として計算した。(1) Solid content concentration For the solid content concentration of each example, 10 g of the sample obtained in each example was used as an infrared moisture meter (manufactured by Kett Science Institute Headquarters, Inc., type FD-720, heating condition 110 ° C./30 minutes). The evaporation residue was calculated as a solid content.
(2)pH
各例で得られた分散液のpHは、25℃においてpHメーター(東亜ディーケーケー(株)製、型式HM−30G)を用いて測定した。(2) pH
The pH of the dispersion obtained in each example was measured at 25 ° C. using a pH meter (manufactured by DKK-TOA CORPORATION, model HM-30G).
(3)粘度
各例で得られた分散液の粘度は、23℃、60rpmにおいて回転粘度計(東機産業(株)製、型式TV25形粘度計)を用いて測定した。(3) Viscosity The viscosity of the dispersion obtained in each example was measured at 23 ° C. and 60 rpm using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., model TV25 type viscometer).
(4)シード粒子の粒径
シード粒子の粒径(ポリアニオンの層の厚さを含む。)は、日機装(株)製マイクロトラックUPA型粒度分布測定装置により測定した。(4) Particle size of seed particles The particle size of seed particles (including the thickness of the polyanion layer) was measured by a Microtrac UPA type particle size distribution measuring device manufactured by Nikkiso Co., Ltd.
(5)ポリスチレンスルホン酸ナトリウムの重量平均分子量
重量平均分子量は、ゲル浸透クロマトグラフィーを用いて測定した。測定には昭和電工(株)製の「Shodex(登録商標) GPC 101」(カラム OHPak SB−806M HQ)を用い、測定条件はカラム温度40℃、溶出液は水、溶出速度1ml/分とした。重量平均分子量を標準ポリスチレン換算分子量(Mw)で表示した。(5) Weight average molecular weight of sodium polystyrene sulfonate The weight average molecular weight was measured by gel permeation chromatography. "Shodex (registered trademark) GPC 101" (column OHPak SB-806M HQ) manufactured by Showa Denko KK was used for the measurement, and the measurement conditions were a column temperature of 40 ° C., an eluate of water, and an elution rate of 1 ml / min. .. The weight average molecular weight was expressed in standard polystyrene equivalent molecular weight (Mw).
(6)固体電解コンデンサ素子の静電容量及び等価直列抵抗
固体電解コンデンサ素子の120Hzでの静電容量(μF)および100kHzでの等価直列抵抗〔ESR〕(mΩ)を、LCRメーター(Agilent製、型式E4980A)を用いて測定した。(6) Capacitance and Equivalent Series Resistance of Solid Electrolytic Capacitor Element The capacitance (μF) of the solid electrolytic capacitor element at 120 Hz and the equivalent series resistance [ESR] (mΩ) at 100 kHz are measured by an LCR meter (manufactured by Agilent). It was measured using model E4980A).
[実施例1]
(ポリアニオンで保護コロイド化されたシード粒子の分散液の作製)
スチレン86g、2−エチルヘキシルアクリレート49g、ジビニルベンゼン15g及びポリスチレンスルホン酸ナトリウム(東ソー有機化学株式会社製、ポリナスPS−5、重量平均分子量:約120,000)22質量%水溶液500gを撹拌混合し、エチレン性不飽和単量体混合液を調製した。一方、ポリスチレンスルホン酸ナトリウム(同上)22質量%水溶液1000gを撹拌しながら、80℃に昇温し、これに過硫酸カリウム2gを添加した。こうして得られた溶液に、前記エチレン性不飽和単量体混合液及び過硫酸カリウム2.5質量%水溶液40gを、それぞれ、2時間及び2.5時間かけて滴下した。滴下終了後、反応液を80℃で2時間保持し、その後、室温(25℃)まで冷却した。得られた反応液に陽イオン交換樹脂(オルガノ株式会社製、IR120B−H)1500ml及び陰イオン交換樹脂(オルガノ株式会社製、IRA410−OH)1500mlを添加し、12時間撹拌した後、イオン交換樹脂をろ別した。ろ液にイオン交換水(以下、単に水と言う。)を添加して固形分濃度が15.0質量%となるように調整し、ポリアニオンで保護コロイド化されたシード粒子(粒径d50:0.46μm)の分散液を得た。[Example 1]
(Preparation of dispersion of seed particles protected and colloidalized with polyanion)
86 g of styrene, 49 g of 2-ethylhexyl acrylate, 15 g of divinylbenzene and 500 g of a 22 mass% aqueous solution of sodium polystyrene sulfonate (Polynas PS-5, weight average molecular weight: about 120,000) manufactured by Tosoh Organic Chemical Co., Ltd. are stirred and mixed, and ethylene is mixed. A sex-unsaturated monomer mixture was prepared. On the other hand, 1000 g of a 22 mass% aqueous solution of sodium polystyrene sulfonate (same as above) was heated to 80 ° C. with stirring, and 2 g of potassium persulfate was added thereto. To the solution thus obtained, 40 g of the ethylenically unsaturated monomer mixed solution and a 2.5 mass% aqueous solution of potassium persulfate were added dropwise over 2 hours and 2.5 hours, respectively. After completion of the dropping, the reaction solution was held at 80 ° C. for 2 hours, and then cooled to room temperature (25 ° C.). To the obtained reaction solution, 1500 ml of a cation exchange resin (IR120B-H manufactured by Organo Corporation) and 1500 ml of an anion exchange resin (IRA410-OH manufactured by Organo Corporation) were added, and the mixture was stirred for 12 hours and then the ion exchange resin. I broke up. Ion-exchanged water (hereinafter, simply referred to as water) is added to the filtrate to adjust the solid content concentration to 15.0% by mass, and seed particles protected and colloidalized with polyanions (particle size d50: 0). A dispersion of .46 μm) was obtained.
(工程(A):重合による共役系導電性重合体の分散液(1)の製造)
ポリエチレン製容器内で、水223.2質量部、ポリスチレンスルホン酸ナトリウム(同上)12質量%水溶液31.5質量部、及び上記のとおり作製したポリアニオンで保護コロイド化されたシード粒子の分散液34.0質量部を32℃で撹拌混合した。この混合液に、32℃で3,4−エチレンジオキシチオフェン2.80質量部を添加して、ホモミキサー(特殊機化工業株式会社製、ロボミックス;4000rpm)で30分間乳化混合し、単量体化合物分散液を調製した。3,4−エチレンジオキシチオフェン1モルに対するスルホ基およびスルホ基の塩からなる基の量は1.9モルであった。なお、前記スルホ基等は、ポリスチレンスルホン酸ナトリウム12質量%水溶液及び前記分散液中のポリスチレンスルホン酸ナトリウム由来のものである。(Step (A): Production of Dispersion Liquid (1) of Conjugated Conductive Polymer by Polymerization)
In a polyethylene container, 223.2 parts by mass of water, 31.5 parts by mass of a 12% by mass aqueous solution of sodium polystyrene sulfonate (same as above), and a dispersion of seed particles protected and colloidalized with the polyanion prepared as described above 34. 0 parts by mass was stirred and mixed at 32 ° C. To this mixed solution, 2.80 parts by mass of 3,4-ethylenedioxythiophene was added at 32 ° C., and the mixture was emulsified and mixed with a homomixer (Robomix manufactured by Tokushu Kika Kogyo Co., Ltd .; 4000 rpm) for 30 minutes. A quantitative compound dispersion was prepared. The amount of the sulfo group and the group consisting of the salt of the sulfo group per 1 mol of 3,4-ethylenedioxythiophene was 1.9 mol. The sulfo groups and the like are derived from a 12% by mass aqueous solution of sodium polystyrene sulfonate and sodium polystyrene sulfonate in the dispersion.
前記単量体化合物分散液291.5質量部を、ハイシェアミキサー(太平洋機工株式会社製、マイルダー(登録商標)303V;5000rpm)及び循環ポンプが接続されたステンレス製容器に投入し、撹拌翼及びハイシェアミキサーにより、32℃で循環させながら撹拌し、前記分散液に酸化剤としてペルオキソ二硫酸ナトリウム5.89質量部及び硫酸鉄(III)六水和物の1質量%水溶液6.88質量部を添加して、24時間重合反応を行うことで、共役系導電性重合体を含む分散液(1−1)を得た。共役系導電性重合体100質量部に対するポリアニオンの使用量は261質量部であった。 291.5 parts by mass of the monomer compound dispersion was put into a stainless steel container to which a high-share mixer (manufactured by Pacific Kiko Co., Ltd., Milder (registered trademark) 303V; 5000 rpm) and a circulation pump were connected, and the stirring blade and the stirring blade were charged. Stir with a high-share mixer while circulating at 32 ° C., and add 5.89 parts by mass of sodium peroxodisulfate and 6.88 parts by mass of a 1% by mass aqueous solution of iron (III) sulfate hexahydrate as an oxidizing agent to the dispersion. Was added and the polymerization reaction was carried out for 24 hours to obtain a dispersion liquid (1-1) containing a conjugated conductive polymer. The amount of the polyanion used with respect to 100 parts by mass of the conjugated conductive polymer was 261 parts by mass.
(工程(A):分散処理による共役系導電性重合体の分散液(2)の製造)
固形分濃度5.80質量%の前記分散液(1−1)に、純水を加えて、固形分濃度4.73質量%、全量1500mLに調整した。その後、分散液(1−1)(以下、前記分散液(1−1)、およびこれに各種操作(純水の添加、高圧分散処理、イオン交換等)を施したものを、区別することなく「分散液(1−1)」と記載する(ただし、最終生成物である分散液(2−1)を除く。)。)を、高圧ホモジナイザー(TWIN PANDA 600、Niro Soavi社製)により分散圧力を400barとして合計45分間高圧分散処理した。この高圧分散処理では、9分間の高圧分散処理と10分間の一時停止とを4回繰り返し、最後に9分間の高圧分散処理を行った。最後の一時停止開始時の分散液(1−1)の粘度は900mPa・s、最後の一時停止終了時の分散液(1−1)の粘度は4500mPa・sと、一時停止開始時の5.0倍であった。その後純水を加えて分散液(1−1)を固形分濃度3.99質量%、全量1500mLに調整し、再度分散液(1−1)を、高圧ホモジナイザーにより400barで一時停止をすることなく135分間高圧分散処理し、その直後に陽イオン交換樹脂100.5gおよび陰イオン交換樹脂87.9gにより3時間イオン交換し、脱塩させた。その後、分散液(1−1)を孔径が5μmのフィルターで濾過した後、さらに孔径が3μmのフィルターで濾過し、純水を加えて固形分濃度1.60質量%に調整することで、pH1.9の、共役系導電性重合体の分散液(2−1)を得た。
工程(A)の概略を図1に示す。(Step (A): Production of Dispersion Liquid (2) of Conjugated Conductive Polymer by Dispersion Treatment)
Pure water was added to the dispersion liquid (1-1) having a solid content concentration of 5.80% by mass to adjust the solid content concentration to 4.73% by mass and the total volume to 1500 mL. After that, the dispersion liquid (1-1) (hereinafter, the dispersion liquid (1-1)) and those subjected to various operations (addition of pure water, high-pressure dispersion treatment, ion exchange, etc.) are not distinguished. The dispersion pressure described as "dispersion liquid (1-1)" (however, excluding the dispersion liquid (2-1) which is the final product) is dispersed by a high-pressure homogenizer (TWIN PANDA 600, manufactured by Niro Soavi). Was 400 bar, and high-pressure dispersion treatment was performed for a total of 45 minutes. In this high-pressure dispersion treatment, a 9-minute high-pressure dispersion treatment and a 10-minute pause were repeated four times, and finally a 9-minute high-pressure dispersion treatment was performed. The viscosity of the dispersion liquid (1-1) at the start of the final pause is 900 mPa · s, and the viscosity of the dispersion liquid (1-1) at the end of the final pause is 4500 mPa · s. It was 0 times. After that, pure water was added to adjust the dispersion liquid (1-1) to a solid content concentration of 3.99% by mass and a total volume of 1500 mL, and the dispersion liquid (1-1) was again subjected to a high-pressure homogenizer at 400 bar without pausing. High-pressure dispersion treatment was carried out for 135 minutes, and immediately after that, ions were exchanged with 100.5 g of a cation exchange resin and 87.9 g of an anion exchange resin for 3 hours for desalting. Then, the dispersion liquid (1-1) is filtered through a filter having a pore size of 5 μm, further filtered through a filter having a pore size of 3 μm, and pure water is added to adjust the solid content concentration to 1.60% by mass to adjust the pH to 1. A dispersion liquid (2-1) of a conjugated conductive polymer of 9. was obtained.
The outline of the step (A) is shown in FIG.
(誘電体酸化被膜を表面に有する多孔性陽極体の形成)
特開2011−77257号公報に記載の方法によって、固体電解コンデンサに用いる、誘電体酸化被膜を表面に有する多孔性陽極体を製造した。すなわち、コンデンサ用ニオブ粉末を用い、陽極体表面に五酸化二ニオブを有する誘電体酸化被膜が形成された陽極リード付きの多孔性陽極体を作製した。この多孔性陽極体の20質量%硫酸中での静電容量は、21.4μFであった。(Formation of a porous anode having a dielectric oxide film on its surface)
A porous anode having a dielectric oxide film on its surface, which is used for a solid electrolytic capacitor, was produced by the method described in JP-A-2011-77257. That is, using niobium powder for a capacitor, a porous anode body with an anode lead having a dielectric oxide film having niobium pentoxide formed on the surface of the anode body was produced. The capacitance of this porous anode in 20% by mass sulfuric acid was 21.4 μF.
(工程(B)及び(C):固体電解コンデンサの作製)
25℃の大気下で、上記方法で得られた多孔性陽極体を、上記共役系導電性重合体の分散液(2−1)に1分間含浸させた後、熱風乾燥器(TABAI製、形式ST−110)により120℃で30分間乾燥させた。この処理を10回繰り返し行い、多孔性陽極体の誘電体酸化被膜の表面に固体電解質層を形成して、固体電解コンデンサを得た。(Steps (B) and (C): Fabrication of solid electrolytic capacitor)
After impregnating the porous anode obtained by the above method with the dispersion liquid (2-1) of the conjugated conductive polymer for 1 minute in the atmosphere of 25 ° C., a hot air dryer (manufactured by TABAI, type) It was dried at 120 ° C. for 30 minutes by ST-110). This process was repeated 10 times to form a solid electrolyte layer on the surface of the dielectric oxide film of the porous anode to obtain a solid electrolytic capacitor.
次いで、固体電解コンデンサに、陽極リード端子に接触させないようにカーボンペーストを塗布し乾燥させ、さらに、陽極・陰極の接点をとるために銀ペーストを塗布し、リードフレーム上で乾燥させた。陽極リード線をリードフレームの陽極リード部に電気的に接続させ樹脂で封止し、これによって固体電解コンデンサ素子を得た。 Next, the solid electrolytic capacitor was coated with a carbon paste so as not to come into contact with the anode lead terminals and dried, and further, a silver paste was applied to make contact between the anode and the cathode and dried on the lead frame. The anode lead wire was electrically connected to the anode lead portion of the lead frame and sealed with a resin to obtain a solid electrolytic capacitor element.
[実施例2]
前記一時停止の時間を一時停止1回あたり30分間に変更したこと以外は実施例1と同様にして固体電解コンデンサ素子を製造した。[Example 2]
A solid electrolytic capacitor element was manufactured in the same manner as in Example 1 except that the pause time was changed to 30 minutes for each pause.
[実施例3]
45分間の高圧分散処理において、6分間の高圧分散処理と10分間の一時停止とを7回繰り返し、最後に3分間の高圧分散処理を行ったこと以外は実施例1と同様にして固体電解コンデンサ素子を製造した。[Example 3]
In the high-voltage dispersion treatment for 45 minutes, the solid electrolytic capacitor was repeated 7 times for 6 minutes and paused for 10 minutes, and finally the high-voltage dispersion treatment for 3 minutes was performed in the same manner as in Example 1. Manufactured the element.
[実施例4]
(工程(B):共役系導電性重合体を含む分散液(1)の製造(シード粒子を含まない))
ポリエチレン製容器内で、水231.0質量部、ポリスチレンスルホン酸ナトリウム12質量%水溶液60.0質量部を32℃で撹拌混合した。この混合液に、32℃で3,4−エチレンジオキシチオフェン2.80質量部を添加して、ホモミキサー(特殊機化工業株式会社製、ロボミックス;4000rpm)で30分間乳化混合し、単量体化合物分散液を調製した。[Example 4]
(Step (B): Production of Dispersion Liquid (1) Containing Conjugated Conductive Polymer (Does Not Contain Seed Particles))
In a polyethylene container, 231.0 parts by mass of water and 60.0 parts by mass of a 12% by mass aqueous solution of sodium polystyrene sulfonate were stirred and mixed at 32 ° C. To this mixed solution, 2.80 parts by mass of 3,4-ethylenedioxythiophene was added at 32 ° C., and the mixture was emulsified and mixed with a homomixer (Robomix manufactured by Tokushu Kika Kogyo Co., Ltd .; 4000 rpm) for 30 minutes. A quantitative compound dispersion was prepared.
前記単量体化合物分散液293.8質量部を、ハイシェアミキサー(太平洋機工株式会社製、マイルダー(登録商標)303V;5000rpm)及び循環ポンプが接続されたステンレス製容器に投入し、撹拌翼及びハイシェアミキサーにより、32℃で循環しながら撹拌し、酸化剤としてペルオキソ二硫酸ナトリウム5.89質量部及び硫酸鉄(III)六水和物の1質量%水溶液6.88質量部を添加して、24時間重合反応を行うことで、共役系導電性重合体を含む分散液(1−4)を得た。
前記分散液(1−1)を前記分散液(1−4)に変更したこと以外は実施例1と同様にして固体電解コンデンサ素子を製造した。293.8 parts by mass of the monomer compound dispersion was put into a stainless steel container to which a high-share mixer (manufactured by Pacific Kiko Co., Ltd., Milder (registered trademark) 303V; 5000 rpm) and a circulation pump were connected, and the stirring blade and Stir while circulating at 32 ° C. with a high-share mixer, and add 5.89 parts by mass of sodium peroxodisulfate and 6.88 parts by mass of a 1% by mass aqueous solution of iron (III) sulfate hexahydrate as an oxidizing agent. , A dispersion liquid (1-4) containing a conjugated conductive polymer was obtained by carrying out a polymerization reaction for 24 hours.
A solid electrolytic capacitor element was manufactured in the same manner as in Example 1 except that the dispersion liquid (1-1) was changed to the dispersion liquid (1-4).
[実施例5]
高圧ホモジナイザーによる高圧分散処理を超音波ホモジナイザーによる分散処理に変更したこと以外は実施例1と同様にして固体電解コンデンサ素子を得た。超音波ホモジナイザーの消費電力は100W/L(リットル)、照射時間は1時間/L(リットル)であった。[Example 5]
A solid electrolytic capacitor element was obtained in the same manner as in Example 1 except that the high-voltage dispersion treatment by the high-voltage homogenizer was changed to the dispersion treatment by the ultrasonic homogenizer. The power consumption of the ultrasonic homogenizer was 100 W / L (liter), and the irradiation time was 1 hour / L (liter).
[実施例6]
高圧分散処理における分散圧力を250barに変更したこと以外は実施例1と同様にして固体電解コンデンサ素子を製造した。[Example 6]
A solid electrolytic capacitor element was manufactured in the same manner as in Example 1 except that the dispersion pressure in the high-voltage dispersion treatment was changed to 250 bar.
[実施例7]
高圧分散処理を施す直前の分散液(1−1)に塩化合物として硫酸アンモニウムを添加したこと以外は実施例1と同様にして固体電解コンデンサ素子を製造した。[Example 7]
A solid electrolytic capacitor element was manufactured in the same manner as in Example 1 except that ammonium sulfate was added as a salt compound to the dispersion liquid (1-1) immediately before the high-pressure dispersion treatment.
[実施例8]
共役系導電性重合体の分散液(2−1)に、電気伝導率向上剤としてエチレングリコールを、分散液(2−1)95質量部に対し5質量部となる割合で添加して共役系導電性重合体の分散液(2−8)を得たこと以外は実施例1と同様にして、固体電解コンデンサ素子を製造した。[Example 8]
Conjugated system Conjugated system by adding ethylene glycol as an electric conductivity improver to the dispersion liquid (2-1) of the conjugated conductive polymer at a ratio of 5 parts by mass with respect to 95 parts by mass of the dispersion liquid (2-1). A solid electrolytic capacitor element was manufactured in the same manner as in Example 1 except that the dispersion liquid (2-8) of the conductive polymer was obtained.
[比較例1]
前記高圧分散処理において前記一時停止を行わなかったこと以外は実施例1と同様にして固体電解コンデンサ素子を製造した。分散液の粘度の測定は、高圧分散処理の開始から36分後に行った。[Comparative Example 1]
A solid electrolytic capacitor element was manufactured in the same manner as in Example 1 except that the suspension was not performed in the high-voltage dispersion treatment. The viscosity of the dispersion was measured 36 minutes after the start of the high-pressure dispersion treatment.
[比較例2]
前記高圧分散処理において前記一時停止を行わなかったこと以外は実施例4と同様にして固体電解コンデンサ素子を製造した。分散液の粘度の測定は、高圧分散処理の開始から36分後に行った。[Comparative Example 2]
A solid electrolytic capacitor element was manufactured in the same manner as in Example 4 except that the suspension was not performed in the high-voltage dispersion treatment. The viscosity of the dispersion was measured 36 minutes after the start of the high-pressure dispersion treatment.
[比較例3]
前記分散処理において前記一時停止を行わなかったこと以外は実施例5と同様にして固体電解コンデンサ素子を製造した。分散液の粘度の測定は、高圧分散処理の開始から36分後に行った。[Comparative Example 3]
A solid electrolytic capacitor element was manufactured in the same manner as in Example 5 except that the suspension was not performed in the dispersion treatment. The viscosity of the dispersion was measured 36 minutes after the start of the high-pressure dispersion treatment.
[比較例4]
前記分散処理において前記一時停止を行わなかったこと以外は実施例6と同様にして固体電解コンデンサ素子を製造した。分散液の粘度の測定は、高圧分散処理の開始から36分後に行った。
実施例1〜8及び比較例1〜4の製造条件および評価結果(静電容量及び等価直列抵抗)を表1に示す。[Comparative Example 4]
A solid electrolytic capacitor element was manufactured in the same manner as in Example 6 except that the suspension was not performed in the dispersion treatment. The viscosity of the dispersion was measured 36 minutes after the start of the high-pressure dispersion treatment.
Table 1 shows the manufacturing conditions and evaluation results (capacitance and equivalent series resistance) of Examples 1 to 8 and Comparative Examples 1 to 4.
表1の結果から、誘電体被膜を有する弁作用金属からなる多孔性陽極体に付着させる工程において、共役系導電性重合体の分散液(2)を使用した実施例1〜8の固体電解コンデンサ素子は、工程(A)において分散処理の一時停止による増粘をさせなかった分散液を用いた比較例1〜4の固体電解コンデンサ素子に比べて容量発現率(静電容量)が高く、かつ等価直列抵抗(ESR)が低いことがわかる。 From the results in Table 1, the solid electrolytic capacitors of Examples 1 to 8 using the dispersion liquid (2) of the conjugated conductive polymer in the step of adhering to the porous anode made of the valve acting metal having a dielectric coating. The element has a higher capacitance expression rate (capacitance) than the solid electrolytic capacitor elements of Comparative Examples 1 to 4 using the dispersion liquid which was not thickened by suspending the dispersion treatment in the step (A). It can be seen that the equivalent series resistance (ESR) is low.
なお、本発明においてはポリアニオンと共役系導電性重合体を含有する分散液(1)を分散処理しているため、分散液(2)から水性媒体を除去して形成された固体電解質層、および固体電解コンデンサが取り得る全ての構造を示すのは非実際的である。 In the present invention, since the dispersion liquid (1) containing the polyanion and the conjugated conductive polymer is dispersed, the solid electrolyte layer formed by removing the aqueous medium from the dispersion liquid (2), and It is impractical to show all possible structures of solid electrolytic capacitors.
Claims (15)
ポリアニオンおよび水性媒体を含む液の中で、共役系導電性重合体を得るための単量体化合物を重合して、共役系導電性重合体を含む分散液(1)を得ると共に、前記分散液(1)に分散処理を施して、前記共役系導電性重合体を含有する分散液(2)を得る工程(A)、
前記分散液(2)を、表面に誘電体被膜を有する弁作用金属からなる多孔性陽極体に付着させる工程(B)、および
前記多孔性陽極体に付着した前記分散液(2)から前記水性媒体を除去し固体電解質層を形成する工程(C)
を有し、
前記工程(A)において、前記分散処理を一時停止する操作を1回以上、合計1〜6000分行い、1回の一時停止時間は1〜300分である、
固体電解コンデンサの製造方法。A method for manufacturing a solid electrolytic capacitor having a porous anode made of a valve acting metal having a dielectric film on its surface and a solid electrolyte layer provided on the surface of the dielectric film.
A monomer compound for obtaining a conjugated conductive polymer is polymerized in a liquid containing a polyanion and an aqueous medium to obtain a dispersion liquid (1) containing the conjugated conductive polymer, and the dispersion liquid is obtained. A step (A) of subjecting (1) to a dispersion treatment to obtain a dispersion liquid (2) containing the conjugated conductive polymer.
The step (B) of adhering the dispersion liquid (2) to a porous anode made of a valve acting metal having a dielectric film on the surface, and the aqueous dispersion liquid (2) adhering to the porous anode body. Step of removing the medium to form a solid electrolyte layer (C)
Have,
In the step (A), the operation of suspending the dispersion processing is performed once or more for a total of 1 to 6000 minutes, and the suspension time of one time is 1 to 300 minutes.
Manufacturing method of solid electrolytic capacitors.
R1及びR2は、R1とR2とが互いに結合して、置換基を有してもよい置換基以外の部分の炭素数が3〜10の脂環、置換基を有してもよい置換基以外の部分の炭素数が6〜10の芳香環、置換基を有してもよい置換基以外の部分の炭素数が2〜10の酸素原子含有複素環、置換基を有してもよい置換基以外の部分の炭素数が2〜10のイオウ原子含有複素環、若しくは置換基を有してもよい置換基以外の部分の炭素数が2〜10のイオウ原子及び酸素原子含有複素環を表す。)
で示される化合物である請求項1〜10のいずれか一項に記載の固体電解コンデンサの製造方法。The monomer compound has the following formula (1).
The method for producing a solid electrolytic capacitor according to any one of claims 1 to 10, which is a compound represented by.
前記工程(A)において、前記分散処理を一時停止する操作を1回以上、合計1〜6000分行い、1回の一時停止時間は1〜300分である
共役系導電性重合体を含有する分散液(2)の製造方法。A monomer compound for obtaining a conjugated conductive polymer is polymerized in a liquid containing a polyanion and an aqueous medium to obtain a dispersion liquid (1) containing the conjugated conductive polymer, and the dispersion liquid is obtained. It has a step (A) of subjecting (1) to a dispersion treatment to obtain a dispersion liquid (2) containing the conjugated conductive polymer.
In the step (A), the operation of suspending the dispersion treatment is performed once or more for a total of 1 to 6000 minutes, and the suspension time of each time is 1 to 300 minutes. Dispersion containing a conjugated conductive polymer Method for producing liquid (2).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018068442 | 2018-03-30 | ||
JP2018068442 | 2018-03-30 | ||
PCT/JP2019/013008 WO2019189257A1 (en) | 2018-03-30 | 2019-03-26 | Method of manufacturing solid electrolytic capacitor, and method of manufacturing dispersion containing conjugated electrically conductive polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JP6770217B2 true JP6770217B2 (en) | 2020-10-14 |
JPWO2019189257A1 JPWO2019189257A1 (en) | 2020-12-03 |
Family
ID=68060053
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020510964A Active JP6770217B2 (en) | 2018-03-30 | 2019-03-26 | A method for producing a solid electrolytic capacitor and a method for producing a dispersion containing a conjugated conductive polymer. |
Country Status (6)
Country | Link |
---|---|
US (1) | US11031187B2 (en) |
EP (1) | EP3780045B1 (en) |
JP (1) | JP6770217B2 (en) |
KR (1) | KR102319989B1 (en) |
CN (1) | CN111937106B (en) |
WO (1) | WO2019189257A1 (en) |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4329299B2 (en) | 2001-07-16 | 2009-09-09 | パナソニック株式会社 | Manufacturing method of solid electrolytic capacitor |
JP3980540B2 (en) | 2003-09-03 | 2007-09-26 | 信越ポリマー株式会社 | Conductive composition and method for producing the same |
JP2005109252A (en) | 2003-09-30 | 2005-04-21 | Nippon Chemicon Corp | Method of manufacturing solid electrolytic capacitor |
JP2007332183A (en) | 2006-06-12 | 2007-12-27 | Yokohama Rubber Co Ltd:The | Method for synthesizing electroconductive polymer, electroconductive polymer, method for producing electroconductive polymer dispersion and electroconductive polymer dispersion |
DE102008005568A1 (en) | 2008-01-22 | 2009-07-23 | H.C. Starck Gmbh | Process for the preparation of conductive polymers |
WO2009131011A1 (en) | 2008-04-21 | 2009-10-29 | テイカ株式会社 | Dispersion of electroconductive composition, electroconductive composition, and use thereof |
DE102008024805A1 (en) * | 2008-05-23 | 2009-12-03 | H.C. Starck Gmbh | Process for the preparation of electrolytic capacitors |
JP2010087401A (en) * | 2008-10-02 | 2010-04-15 | Shin Etsu Polymer Co Ltd | Method for manufacturing capacitor |
JP5341699B2 (en) | 2009-09-30 | 2013-11-13 | 昭和電工株式会社 | Manufacturing method of solid electrolytic capacitor |
EP2543688A4 (en) * | 2010-03-01 | 2018-04-25 | Nippon Chemi-Con Corporation | Polymerization fluid, process for production thereof, transparent film made from the polymerization fluid, and transparent electrode |
JP2012191178A (en) * | 2011-02-22 | 2012-10-04 | Sanyo Electric Co Ltd | Electrolytic capacitor and manufacturing method of the same |
CN103460320B (en) * | 2011-04-13 | 2016-10-19 | 松下知识产权经营株式会社 | The manufacture method of electroconductive polymer dispersion soln and electrolysis condenser |
JP5939454B2 (en) | 2011-09-06 | 2016-06-22 | 日本ケミコン株式会社 | Method for producing dispersion for solid electrolytic capacitor and method for producing solid electrolytic capacitor |
WO2013035640A1 (en) * | 2011-09-06 | 2013-03-14 | 日本ケミコン株式会社 | Method of manufacturing a liquid dispersion for a solid electrolyte capacitor, liquid dispersion for a solid electrolyte capacitor, method of manufacturing a solid electrolyte capacitor employing this liquid dispersion, and solid electrolyte capacitor |
DE102013213720A1 (en) * | 2012-07-19 | 2014-01-23 | Avx Corporation | Temperature stable solid electrolytic capacitor |
DE102012018978A1 (en) * | 2012-09-27 | 2014-03-27 | Heraeus Precious Metals Gmbh & Co. Kg | Use of PEDOT / PSS dispersions with high PEDOT content for the production of capacitors and solar cells |
KR101782434B1 (en) * | 2013-04-05 | 2017-09-28 | 쇼와 덴코 가부시키가이샤 | Method for manufacturing solid electrolytic capacitor |
US10049822B2 (en) * | 2013-09-11 | 2018-08-14 | Tayca Corporation | Monomer liquid for of conductive polymer production and a manufacturing method of an electrolyte capacitor using the same |
JP2016082052A (en) * | 2014-10-16 | 2016-05-16 | Necトーキン株式会社 | Conductive polymer solution, conductive polymer composition, electrolytic capacitor, and production method thereof |
KR102101183B1 (en) * | 2015-12-28 | 2020-04-16 | 쇼와 덴코 가부시키가이샤 | Method for producing a dispersion containing a conductive polymer |
CN107540852B (en) * | 2017-07-27 | 2020-07-14 | 西北工业大学 | Method for preparing particles with core-shell structure and hollow particles by ultrasonic field |
-
2019
- 2019-03-26 KR KR1020207029561A patent/KR102319989B1/en active IP Right Grant
- 2019-03-26 JP JP2020510964A patent/JP6770217B2/en active Active
- 2019-03-26 CN CN201980023948.XA patent/CN111937106B/en active Active
- 2019-03-26 WO PCT/JP2019/013008 patent/WO2019189257A1/en active Application Filing
- 2019-03-26 US US17/043,331 patent/US11031187B2/en active Active
- 2019-03-26 EP EP19776760.1A patent/EP3780045B1/en active Active
Also Published As
Publication number | Publication date |
---|---|
US11031187B2 (en) | 2021-06-08 |
CN111937106B (en) | 2021-09-07 |
KR20200122402A (en) | 2020-10-27 |
US20210027953A1 (en) | 2021-01-28 |
KR102319989B1 (en) | 2021-11-02 |
WO2019189257A1 (en) | 2019-10-03 |
EP3780045A4 (en) | 2022-01-19 |
CN111937106A (en) | 2020-11-13 |
EP3780045B1 (en) | 2023-03-08 |
JPWO2019189257A1 (en) | 2020-12-03 |
EP3780045A1 (en) | 2021-02-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6539913B2 (en) | Method of manufacturing solid electrolytic capacitor | |
JP7552775B2 (en) | Conjugated conductive polymer-containing dispersion and method for producing solid electrolytic capacitor | |
JP7238793B2 (en) | Dispersion composition for manufacturing solid electrolytic capacitor and method for manufacturing solid electrolytic capacitor | |
WO2017115607A1 (en) | Process for producing dispersion containing electroconductive polymer | |
JP7131941B2 (en) | Method for producing dispersion containing conjugated conductive polymer, method for producing solid electrolytic capacitor, and solid electrolytic capacitor | |
JP6770217B2 (en) | A method for producing a solid electrolytic capacitor and a method for producing a dispersion containing a conjugated conductive polymer. | |
WO2023119762A1 (en) | Method for producing polymer dispersion for solid electrolytic capacitor, and method for producing solid electrolytic capacitor | |
JP2024089375A (en) | Manufacturing method of solid electrolytic capacitor | |
TW202432739A (en) | Dispersion containing conductive polymer, solid electrolytic capacitor and method for producing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200716 |
|
A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20200716 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200729 |
|
A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20200731 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200915 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200924 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6770217 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |